Oxide Sintered Material, Method of Producing Oxide Sintered Material, Sputtering Target, and Method of Producing Semiconductor Device

ABSTRACT

The present invention relates to an oxide sintered material that can be used suitably as a sputtering target for forming an oxide semiconductor film using a sputtering method, a method of producing the oxide sintered material, a sputtering target including the oxide sintered material, and a method of producing a semiconductor device  10  including an oxide semiconductor film  14  formed using the oxide sintered material.

TECHNICAL FIELD

The present invention relates to: an oxide sintered material that can be used suitably as a sputtering target for forming an oxide semiconductor film using a sputtering method; a method of producing the oxide sintered material; a sputtering target including the oxide sintered material; and a method of producing a semiconductor device including an oxide semiconductor film formed using the sputtering target by the sputtering method. The present application claims a priority based on Japanese Patent Application No. 2017-028972 filed on Feb. 20, 2017, the entire content of which is incorporated herein by reference.

BACKGROUND ART

Conventionally, an amorphous silicon (a-Si) film has been used mainly for a semiconductor film serving as a channel layer of a TFT (thin film transistor), which is a semiconductor device, in a liquid crystal display device, a thin film EL (electroluminescence) display device, an organic EL display device, or the like.

In recent years, as a material to replace a-Si, a complex oxide containing indium (In), gallium (Ga), and zinc (Zn), i.e., an In—Ga—Zn-based complex oxide (also referred to as “IGZO”) has been drawing attention. Such an IGZO-based oxide semiconductor can be expected to have higher carrier mobility than that in a-Si.

For example, Japanese Patent Laying-Open No. 2008-199005 (Patent Literature 1) discloses that an oxide semiconductor film mainly composed of IGZO is formed through a sputtering method employing an oxide sintered material as a target.

Japanese Patent Laying-Open No. 2008-192721 (Patent Literature 2) discloses an oxide sintered material containing In and tungsten (W) as materials suitably used in forming an oxide semiconductor film by the sputtering method or the like.

Moreover, Japanese Patent Laying-Open No. 09-071860 (Patent Literature 3) discloses an oxide sintered material containing In and Zn.

CITATION LIST Patent Literature

-   PTL 1: Japanese Patent Laying-Open No. 2008-199005 -   PTL 2: Japanese Patent Laying-Open No. 2008-192721 -   PTL 3: Japanese Patent Laying-Open No. 09-071860 -   PTL 4: Japanese Patent Laying-Open No. 2008-163441

SUMMARY OF INVENTION

An oxide sintered material according to one embodiment of the present invention is an oxide sintered material containing indium, tungsten, and zinc, the oxide sintered material including: a first crystal phase that is a main component of the oxide sintered material and includes a bixbyite type crystal phase; and a second crystal phase having a first diffraction peak at a location of more than 34.74 deg and less than 34.97 deg of 2θ in X-ray diffraction, wherein the oxide sintered material has an apparent density of more than 6.4 g/cm³ and less than or equal to 7.5 g/cm³, a content of the tungsten relative to a total of the indium, the tungsten, and the zinc in the oxide sintered material is more than 0.01 atom % and less than or equal to 5.0 atom %, a content of the zinc relative to the total of the indium, the tungsten, and the zinc in the oxide sintered material is more than or equal to 1.2 atom % and less than 50 atom %, and an atomic ratio of the zinc to the tungsten in the oxide sintered material is more than 1.0 and less than 20000.

A sputtering target according to another embodiment of the present invention includes the oxide sintered material of the foregoing embodiment.

A method of producing a semiconductor device according to still another embodiment of the present invention is a method of producing a semiconductor device including an oxide semiconductor film, the method including: preparing the sputtering target of the foregoing embodiment; and forming the oxide semiconductor film by a sputtering method using the sputtering target.

A method of producing an oxide sintered material according to yet another embodiment of the present invention is a method of producing the oxide sintered material of the foregoing embodiment, the method including: preparing a primary mixture of an indium oxide powder and a tungsten oxide powder; forming a calcinated powder by heating the primary mixture; preparing a secondary mixture of source powders including the calcinated powder; forming a molded body by molding the secondary mixture; and forming an oxide sintered material by sintering the molded body, wherein the forming of the calcinated powder includes forming a powder of a complex oxide including indium and tungsten as the calcinated powder by heating the primary mixture at a temperature of more than or equal to 700° C. and less than 1400° C. in an oxygen-containing atmosphere.

A method of producing an oxide sintered material according to still another embodiment of the present invention is a method of producing the oxide sintered material of the foregoing embodiment, the method including: preparing a primary mixture of a zinc oxide powder and a tungsten oxide powder; forming a calcinated powder by heating the primary mixture; preparing a secondary mixture of source powders including the calcinated powder; forming a molded body by molding the secondary mixture; and forming an oxide sintered material by sintering the molded body, wherein the forming of the calcinated powder includes forming a powder of a complex oxide including zinc and tungsten as the calcinated powder by heating the primary mixture at a temperature of more than or equal to 550° C. and less than 1200° C. in an oxygen-containing atmosphere.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A is a schematic plan view showing an exemplary semiconductor device according to one embodiment of the present invention.

FIG. 1B is a schematic cross sectional view along an IB-IB line shown in FIG. 1A.

FIG. 2 is a schematic cross sectional view showing another exemplary semiconductor device according to one embodiment of the present invention.

FIG. 3 is a schematic cross sectional view showing still another exemplary semiconductor device according to one embodiment of the present invention.

FIG. 4A is a schematic cross sectional view showing an exemplary method of producing the semiconductor device shown in FIG. 1A and FIG. 1B.

FIG. 4B is a schematic cross sectional view showing an exemplary method of producing the semiconductor device shown in FIG. 1A and FIG. 1B.

FIG. 4C is a schematic cross sectional view showing an exemplary method of producing the semiconductor device shown in FIG. 1A and FIG. 1B.

FIG. 4D is a schematic cross sectional view showing an exemplary method of producing the semiconductor device shown in FIG. 1A and FIG. 1B.

FIG. 5A is a schematic cross sectional view showing an exemplary method of producing the semiconductor device shown in FIG. 2.

FIG. 5B is a schematic cross sectional view showing an exemplary method of producing the semiconductor device shown in FIG. 2.

FIG. 5C is a schematic cross sectional view showing an exemplary method of producing the semiconductor device shown in FIG. 2.

FIG. 5D is a schematic cross sectional view showing an exemplary method of producing the semiconductor device shown in FIG. 2.

DETAILED DESCRIPTION Problems to be Solved by the Present Disclosure

A TFT including the IGZO-based oxide semiconductor film described in Patent Literature 1 as a channel layer has a low field effect mobility of about 10 cm²/Vs, disadvantageously.

Moreover, Patent Literature 2 proposes a TFT including, as a channel layer, an oxide semiconductor film formed using an oxide sintered material including In and W; however, reliability of the TFT has not been examined.

A thin film formed using the oxide sintered material described in Patent Literature 3 is a transparent conductive film, and has a lower electric resistance than that of a semiconductor film such as a thin film used for a channel layer of a TFT, for example. Moreover, when an oxide sintered material is used as a sputtering target, the oxide sintered material is required to have a high density (apparent density); however, the apparent density of the oxide sintered material described in Patent Literature 3 cannot be made high without setting a sintering temperature to be high when preparing it. However, when the sintering temperature is set to a high temperature, temperature increasing time and temperature decreasing time become long and an amount of electric power also becomes large in order to maintain the sintering atmosphere at the high temperature, thus resulting in decreased productivity. Moreover, the high sintering temperature leads to evaporation of tungsten oxide of the source material, with the result that an oxide sintered material containing W is not obtained.

When an oxide sintered material is applied to a sputtering target, the sputtering target is generally processed into a desired shape through grinding, cutting, or the like. Patent Literature 4 describes that the surface roughness of a sputtering target is reduced upon producing the sputtering target. However, actually, the surface thereof immediately after producing the target is etched by sputtering during use, with the result that the sputtering target is continued to be used with the surface roughness formed while being etched during use. When the roughness of the etched target surface is large, the roughness of a film obtained by sputtering the target also becomes large. When the surface of the obtained film is rough, different types of subsequently formed thin films, such as a source electrode, a drain electrode, a gate insulating film, and an etch stopper layer, are likely to be detached and characteristics of the semiconductor device may be deteriorated. Thus, in order to reduce the surface roughness of the obtained film, it is desired to reduce the surface roughness of the sputtering target during sputtering.

The present invention has an object to provide: an oxide sintered material that can exhibit a high apparent density even with a comparatively small sintering temperature and that can attain a small surface roughness of a sputtering target during sputtering when applied to the sputtering target; a method of producing the oxide sintered material, a sputtering target including the oxide sintered material; and a method of producing a semiconductor device including an oxide semiconductor film formed using the sputtering target.

Advantageous Effect of the Present Disclosure

According to the description above, there can be provided: an oxide sintered material that can exhibit a high apparent density even with a comparatively small sintering temperature and that can attain a small surface roughness of a sputtering target during sputtering when applied to the sputtering target; and a method of producing the oxide sintered material. Moreover, according to the description above, there can be provided a semiconductor device having high field effect mobility as well as high reliability under irradiation of light.

Description of Embodiments

First, embodiments of the present invention are listed and described.

[1] An oxide sintered material according to one embodiment of the present invention is an oxide sintered material containing indium (In), tungsten (W), and zinc (Zn), and includes: a first crystal phase that is a main component of the oxide sintered material and includes a bixbyite type crystal phase; and a second crystal phase having a first diffraction peak at a location of more than 34.74 deg and less than 34.97 deg of 2θ in X-ray diffraction. The second crystal phase is included in a part of the oxide sintered material. The oxide sintered material of the present embodiment has an apparent density of more than 6.4 g/cm³ and less than or equal to 7.5 g/cm³, a content (hereinafter, also referred to as “W content” of the oxide sintered material) of the W relative to a total of the In, the W, and the Zn in the oxide sintered material is more than 0.01 atom % and less than or equal to 5.0 atom %, a content (hereinafter, also referred to as “Zn content” of the oxide sintered material) of the Zn relative to the total of the In, the W, and the Zn in the oxide sintered material is more than or equal to 1.2 atom % and less than 50 atom %, and an atomic ratio (hereinafter, also referred to as “Zn/W ratio” of the oxide sintered material) of the Zn to the W in the oxide sintered material is more than 1.0 and less than 20000.

According to the oxide sintered material of the present embodiment, it is possible to exhibit a high apparent density (the term “apparent density” means an apparent density after sintering and is also referred to as “sintered density”) even with a comparatively low sintering temperature, and it is possible to attain a small surface roughness of a sputtering target during sputtering when applied to the sputtering target. The apparent density falling within the above range is advantageous in using the oxide sintered material of the present embodiment as a sputtering target. The oxide sintered material of the present embodiment can be used suitably as a sputtering target for forming an oxide semiconductor film (for example, an oxide semiconductor film serving as a channel layer) included in a semiconductor device. According to the oxide sintered material of the present embodiment, an oxide semiconductor film having a small surface roughness can be formed. Moreover, according to the oxide sintered material of the present embodiment, it is possible to obtain a semiconductor device having high field effect mobility as well as high reliability under irradiation of light.

[2] The oxide sintered material of the present embodiment can include a third crystal phase, which is a crystal phase different from the first crystal phase and contains the zinc. The third crystal phase preferably includes particles having an average major axis size of more than or equal to 3 μm and less than or equal to 50 μm and having an average aspect ratio of more than or equal to 1.5 and less than or equal to 50. This is advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target. This is also advantageous in improving field effect mobility of the semiconductor device as well as reliability of the semiconductor device under irradiation of light.

[3] In the oxide sintered material of the present embodiment, the third crystal phase is preferably dispersed in the first crystal phase. This is advantageous in using the oxide sintered material of the present embodiment as a sputtering target.

[4] In the oxide sintered material of the present embodiment, the third crystal phase can include a fourth crystal phase having a second diffraction peak at a location of more than 31.77 deg and less than 32.00 deg of 2θ in the X-ray diffraction. The fourth crystal phase is a phase that can be included in a part of the oxide sintered material. The inclusion of the fourth crystal phase is advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target. The inclusion of the fourth crystal phase is also advantageous in improving field effect mobility of the semiconductor device as well as reliability of the semiconductor device under irradiation of light.

[5] In the oxide sintered material of the present embodiment, a ratio Ia/Ib of a peak intensity Ia of the first diffraction peak to a peak intensity Ib of the second diffraction peak can be more than or equal to 0.05 and less than or equal to 3. Ia/Ib of more than or equal to 0.05 and less than or equal to 3 is advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target. Ia/Ib of more than or equal to 0.05 and less than or equal to 3 is also advantageous in improving field effect mobility of the semiconductor device as well as reliability of the semiconductor device under irradiation of light.

[6] In the oxide sintered material of the present embodiment, the third crystal phase can include a fifth crystal phase, which is a zinc tungstate compound crystal phase. This is advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target. This is also advantageous in improving field effect mobility of the semiconductor device as well as reliability of the semiconductor device under irradiation of light.

[7] In the oxide sintered material of the present embodiment, the first crystal phase can further include an indium tungstate compound crystal phase. This is advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target. This is also advantageous in improving field effect mobility of the semiconductor device as well as reliability of the semiconductor device under irradiation of light.

[8] A sputtering target according to another embodiment of the present invention includes the oxide sintered material of the foregoing embodiment. According to the sputtering target of the present embodiment, the surface roughness of the sputtering target during sputtering can be made small, with the result that the surface roughness of a formed oxide semiconductor film can be made small. Since the sputtering target of the present embodiment includes the oxide sintered material of the foregoing embodiment, the sputtering target is used suitably to form, by the sputtering method, an oxide semiconductor film of a semiconductor device having high field effect mobility as well as high reliability under irradiation of light.

[9] A method of producing a semiconductor device according to still another embodiment of the present invention is a method of producing a semiconductor device including an oxide semiconductor film, the method including: preparing the sputtering target of the foregoing embodiment; and forming the oxide semiconductor film by a sputtering method using the sputtering target. Since the semiconductor device obtained by the production method of the present embodiment includes the oxide semiconductor film formed by the sputtering method using the sputtering target of the foregoing embodiment, the semiconductor device can have an oxide semiconductor film having a small surface roughness and can exhibit high field effect mobility as well as high reliability under irradiation of light. Although the semiconductor device described herein should not be limited particularly, a suitable example thereof is a TFT (thin film transistor) including, as a channel layer, the oxide semiconductor film formed by the sputtering method using the sputtering target of the foregoing embodiment.

[10] In the method of producing the semiconductor device according to the present embodiment, a content of the W (hereinafter, also referred to as “W content” of the oxide semiconductor film) relative to the total of the In, the W, and the Zn in the obtained oxide semiconductor film is preferably more than 0.01 atom % and less than or equal to 5.0 atom %, a content of the Zn (hereinafter, also referred to as “Zn content” of the oxide semiconductor film) relative to the total of the In, the W, and the Zn in the oxide semiconductor film is preferably more than or equal to 1.2 atom % and less than 50 atom %, and an atomic ratio (hereinafter, also referred to as “Zn/W ratio” of the oxide semiconductor film) of the Zn to the W in the oxide semiconductor film is preferably more than 1.0 and less than 20000. Since the semiconductor device obtained by the production method of the present embodiment includes the oxide semiconductor film formed using the sputtering target of the foregoing embodiment, high field effect mobility as well as high reliability under irradiation of light can be exhibited.

[11] In the method of producing the semiconductor device according to the present embodiment, the obtained oxide semiconductor film can be composed of at least one of a nano crystal oxide and an amorphous oxide. This is advantageous in improving field effect mobility as well as reliability under irradiation of light in a semiconductor device including the oxide semiconductor film as a channel layer, for example.

[12] A method of producing an oxide sintered material according to yet another embodiment of the present invention is a method of producing the oxide sintered material of the foregoing embodiment, the method including: preparing a primary mixture of an indium oxide powder and a tungsten oxide powder; forming a calcinated powder by heating the primary mixture; preparing a secondary mixture of source powders including the calcinated powder; forming a molded body by molding the secondary mixture; and forming an oxide sintered material by sintering the molded body, wherein the forming of the calcinated powder includes forming a powder of a complex oxide including indium and tungsten as the calcinated powder by heating the primary mixture at a temperature of more than or equal to 700° C. and less than 1400° C. in an oxygen-containing atmosphere. According to the method of producing the oxide sintered material in the present embodiment, it is possible to comparatively readily obtain an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature, that can be used suitably as a sputtering target, and that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target.

[13] In the method of producing the oxide sintered material according to the embodiment recited in [12], the complex oxide can include an In₆WO₁₂ type crystal phase. This is advantageous in obtaining an oxide sintered material that has a high apparent density and that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target.

[14] A method of producing an oxide sintered material according to yet another aspect of the present invention is a method of producing the oxide sintered material of the foregoing embodiment, the method including: preparing a primary mixture of a zinc oxide powder and a tungsten oxide powder; forming a calcinated powder by heating the primary mixture; preparing a secondary mixture of source powders including the calcinated powder; forming a molded body by molding the secondary mixture; and forming an oxide sintered material by sintering the molded body, wherein the forming of the calcinated powder includes forming a powder of a complex oxide including zinc and tungsten as the calcinated powder by heating the primary mixture at a temperature of more than or equal to 550° C. and less than 1200° C. in an oxygen-containing atmosphere. According to the method of producing the oxide sintered material in the present embodiment, it is possible to comparatively readily obtain an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature, that can be used suitably as a sputtering target, and that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target.

[15] In the method of producing the oxide sintered material according to the embodiment recited in [14], the complex oxide can include a ZnWO₄ type crystal phase. This is advantageous in obtaining an oxide sintered material that has a high apparent density and that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target.

[16] In the method of producing the oxide sintered material according to the embodiment recited in each of [12] to [15], the tungsten oxide powder can include at least one crystal phase selected from a group consisting of a WO₃ crystal phase, a WO₂ crystal phase, and a WO_(2.72) crystal phase. This is advantageous in obtaining an oxide sintered material that has a high apparent density and that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target, and is also advantageous in improving field effect mobility as well as reliability under irradiation of light in a semiconductor device including the oxide semiconductor film as a channel layer, for example.

[17] In the method of producing the oxide sintered material according to the embodiment recited in each of [12] to [16], the tungsten oxide powder can have a median particle size d50 of more than or equal to 0.1 μm and less than or equal to 4 pin. This is advantageous in obtaining an oxide sintered material that has a high apparent density and that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target.

Details of Embodiments of the Present Invention First Embodiment: Oxide Sintered Material

An oxide sintered material of the present embodiment is an oxide sintered material containing indium (In), tungsten (W), and zinc (Zn). The oxide sintered material of the present embodiment includes: a first crystal phase that is a main component of the oxide sintered material and includes a bixbyite type crystal phase; and a second crystal phase having a first diffraction peak at a location of more than 34.74 deg and less than 34.97 deg of 2θ in X-ray diffraction. The second crystal phase is included in a part of the oxide sintered material. The oxide sintered material of the present embodiment has an apparent density of more than 6.4 g/cm³ and less than or equal to 7.5 g/cm³, has a W content of more than 0.01 atom % and less than or equal to 5.0 atom %, and has a Zn content of more than or equal to 1.2 atom % and less than 50 atom %, and a Zn/W ratio is more than 1.0 and less than 20000.

The oxide sintered material of the present embodiment can be used suitably as a sputtering target for forming an oxide semiconductor film (for example, an oxide semiconductor film serving as a channel layer) of a semiconductor device. According to the oxide sintered material of the present embodiment, when applied to a sputtering target, the surface roughness of the sputtering target during sputtering can be made small. Moreover, according to the oxide sintered material of the present embodiment, an oxide semiconductor film having a small surface roughness can be formed. Further, according to the oxide sintered material of the present embodiment, it is possible to obtain a semiconductor device having high field effect mobility as well as high reliability under irradiation of light.

(1) First Crystal Phase

The first crystal phase is a below-described high-content indium type crystal phase, which is a main component of the oxide sintered material and includes at least the bixbyite type crystal phase. In the present specification, the term “bixbyite type crystal phase” is a general term encompassing a bixbyite crystal phase and a phase in which at least one of metallic elements other than In is included in at least a part of the bixbyite crystal phase and which has the same crystal structure as that of the bixbyite crystal phase. The bixbyite crystal phase is one of crystal phases of indium oxide (In₂O₃), represents a crystal structure defined in 6-0416 of the JCPDS card, and is also referred to as “C type rare earth oxide phase” (or “C rare earth structure phase”).

The inclusion of the bixbyite type crystal phase can be identified through X-ray diffraction. Specifically, existence of the bixbyite type crystal phase is confirmed through X-ray diffraction, whereby each plane spacing can be measured. For measurement conditions for the X-ray diffraction, conditions indicated in “(2) Second Crystal Phase” below are employed.

The expression “the first crystal phase including the bixbyite type crystal phase is the main component of the oxide sintered material” is intended to mean that a ratio (high-content indium type crystal phase ratio) of the high-content indium type crystal phase having a high content of In, such as the bixbyite type crystal phase or an indium tungstate compound crystal phase, is more than or equal to 50% in the oxide sintered material.

The “high-content indium type crystal phase ratio” is identified as follows. First, a sample is extracted from a portion of the oxide sintered material, and a surface of this sample is polished to smooth a surface thereof. Next, SEM-EDX (Scanning Secondary Electron Microscope with Energy Dispersive X-ray Fluorescent Emission Spectrometer) is employed to observe the surface of the sample by SEM (Scanning Secondary Electron Microscope) and analyze a composition ratio of metallic elements in each crystal particle by EDX (Energy Dispersive X-ray Fluorescent Emission Spectrometer). Then, the crystal particles are classified into groups based on a tendency of the composition ratios of the metallic elements of those crystal particles. Specifically, the crystal particles are classified into: a group A of crystal particles containing Zn, more typically, having a higher Zn content (content (atom %) of Zn relative to a total of In, W, and Zn) than that of a below-described group B; and group B (high-content indium type crystal phase) of crystal particles having a very low Zn content or containing no Zn and having a higher In content (content (atom %) of In relative to the total of In, W, and Zn) than that of group A. In doing so, the crystal particles of group B are determined as the first crystal phase (In₂O₃ phase or the like). The first crystal phase can include not only the bixbyite type crystal phase but also the indium tungstate compound crystal phase or the like. Further, the “high-content indium type crystal phase ratio” in the oxide sintered material is defined as a ratio (percentage) of an area of the high-content indium type crystal phase (group B) in the surface of the oxide sintered material for which the above-described measurement has been performed. In the oxide sintered material according to the present embodiment thus including the first crystal phase (high-content indium type crystal phase) as the main component, the high-content indium type crystal phase ratio in accordance with this definition is more than or equal to 50%.

In at least a part of the first crystal phase, W and/or Zn may be dissolved in a solid state. When W and/or Zn are dissolved in a solid state in at least a part of the bixbyite type crystal phase included in the first crystal phase in the oxide sintered material according to the present embodiment, the plane spacing becomes wider or narrower than the plane spacing defined in 6-0416 of the JCPDS card. In the X-ray diffraction, a peak location is shifted to the high angle side or is shifted to the low angle side. When such a peak shift is confirmed and existence of a region having In and W and/or Zn mixed therein is confirmed through a surface analysis using SEM-EDX (Scanning Secondary Electron Microscope with Energy Dispersive X-Ray Fluorescent Emission Spectrometer) or TEM-EDX (Transmission Type Secondary Electron Microscope with Energy Dispersive X-Ray Fluorescent Emission Spectrometer), it can be determined that W and/or Zn are dissolved in a solid state in the bixbyite type crystal phase included in the first crystal phase.

Alternatively, when the existence of In and W and/or Zn is confirmed by identifying elements therein through ICP (Inductively Coupled Plasma) mass spectrometry, SEM-EDX, or other element identification methods but oxide(s) of W and/or Zn are not confirmed in the X-ray diffraction, it can also be determined that W and/or Zn are dissolved in a solid state in the bixbyite type crystal phase included in the first crystal phase.

The first crystal phase can further include the indium tungstate compound crystal phase. In X-ray diffraction measurement under conditions shown in “(2) Second Crystal Phase” below, a peak intensity ratio (1122/1400) of a peak intensity 1122 of a (122) plane of the indium tungstate compound to a peak intensity 1400 of a (400) plane of the bixbyite type crystal phase is normally more than or equal to 0 and less than or equal to 0.3. The peak intensity ratio is preferably more than or equal to 0 and less than or equal to 0.1 because this is advantageous in realizing an oxide sintered material that attains a small surface roughness of a sputtering target during sputtering when applied to the sputtering target.

In the present specification, the “indium tungstate compound crystal phase” is a crystal phase having In, W, and O as its main components. Examples thereof include an In₆WO₁₂ crystal phase, an InW₃O₉ crystal phase, and the like. The In₆WO₁₂ crystal phase is an indium tungstate compound crystal phase having a trigonal crystal structure and having a crystal structure defined in 01-074-1410 of the JCPDS card. As long as the crystal structure is exhibited, oxygen may lack or a metal may be dissolved in a solid state to result in a change in lattice constant. The InW₃O₉ crystal phase is an indium tungstate compound crystal phase having a hexagonal crystal structure and a crystal structure defined in 33-627 of the JCPDS card. As long as the crystal structure is exhibited, oxygen may lack or a metal may be dissolved in a solid state to result in a change in lattice constant.

The existence of the indium tungstate compound crystal phase can be confirmed by existence of a peak belonging to the indium tungstate compound crystal phase in the X-ray diffraction. For example, the existence of the indium tungstate compound crystal phase can be confirmed by existence of a peak belonging to the In₆WO₁₂ crystal phase or InW₃O₉ crystal phase. For measurement conditions for the X-ray diffraction, conditions indicated in “(2) Second Crystal Phase” below are employed.

(2) Second Crystal Phase

The second crystal phase is a crystal phase different from the first crystal phase, and has a first diffraction peak at a location of more than 34.74 deg and less than 34.97 deg of 2θ in X-ray diffraction. The oxide sintered material of the present embodiment including the first crystal phase and the second crystal phase different therefrom can exhibit a high apparent density even with a comparatively low sintering temperature and can attain a small surface roughness of a sputtering target during sputtering. In order to obtain the apparent density and the small surface roughness of the sputtering target during sputtering, the location of the first diffraction peak is preferably less than 34.90 deg of 2θ. The second crystal phase is included in a part of the oxide sintered material.

Existence of the second crystal phase can be confirmed through X-ray diffraction. The X-ray diffraction is measured under the following conditions or equivalent conditions.

(Measurement Conditions for X-Ray Diffraction)

θ-2θ method,

X-ray source: Cu Kα rays,

X-ray tube voltage: 45 kV,

X-ray tube current: 40 mA,

Step width: 0.03 deg,

Step time: 1 second/step,

Measurement range 2θ: 10 deg to 90 deg.

The first diffraction peak observed at the location of more than 34.74 deg and less than 34.97 deg of 2θ in X-ray diffraction means that plane spacing is more than 2.56 Å and less than 2.58 Å. It has been found that the first diffraction peak does not coincide with the diffraction peak location of an oxide or complex oxide constituted of an oxygen atom and one or more of In, W. and Zn. Examples of the oxide include: an In₂O₃ phase, which is a bixbyite type crystal phase; a hexagonal wurtzite type crystal ZnO; monoclinic WO₃; and the like. Examples of the complex oxide include: ZnWO₄; In₆WO₁₂; In₂O₃ (ZnO)_(m) (m is a natural number); and the like. The oxide sintered material of the present embodiment further including the second crystal phase having the first diffraction peak that does not coincide with the diffraction peak location of the above-described oxide or complex oxide and that is located within the range of more than 34.74 deg and less than 34.97 deg of 2θ in X-ray diffraction can exhibit a high apparent density even with a comparatively low sintering temperature and can attain a small surface roughness of a sputtering target during sputtering. According to the oxide sintered material, field effect mobility and reliability under irradiation of light can be improved in a semiconductor device including, as a channel layer, an oxide semiconductor film formed using the oxide sintered material.

(3) Apparent Density, W Content, Zn Content, and Zn/W Ratio of Oxide Sintered Material

The oxide sintered material of the present embodiment has an apparent density of more than 6.4 g/cm³ and less than or equal to 7.5 g/cm³. Moreover, in the oxide sintered material of the present embodiment, a relative density, which is a ratio (apparent density/theoretical density) of the apparent density to a theoretical density thereof, is preferably more than or equal to 94%. The theoretical density of the oxide sintered material of the present embodiment depends on the In content, the W content, and the Zn content, and has a value falling within a range of 6.8 g/cm³ to 7.5 g/cm^(r) for calculation.

The apparent density falling within the above range is advantageous in using the oxide sintered material of the present embodiment as a sputtering target. When the oxide sintered material is used as a sputtering target, it is considered more desirable for the oxide sintered material to have a higher apparent density. A low apparent density of an oxide sintered material means that the oxide sintered material has a multiplicity of holes therein. During use of a sputtering target, a surface of the sputtering target is etched by argon ions. Hence, if there are holes in the oxide sintered material, these holes are exposed during film formation to release gas therein, with the result that the gas thus released from the target is mixed in an oxide semiconductor thin film to be deposited. Accordingly, film characteristics are deteriorated. Moreover, it is known that if the apparent density of the oxide sintered material is low, an In insulator referred to as “nodule” is generated on the target during the film formation to hinder favorable sputtering discharge. Also in view of this, it is desirable to increase the apparent density of the oxide sintered material

The oxide sintered material of the present embodiment has a W content of more than 0.01 atom % and less than or equal to 5.0 atom %, a Zn content of more than or equal to 1.2 atom % and less than 50 atom %, and a Zn/W ratio of more than 1.0 and less than 20000. The W content, Zn content, and Zn/W ratio falling within the above respective ranges are advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering, and are also advantageous in improving field effect mobility as well as reliability under irradiation of light in a semiconductor device including, as a channel layer, an oxide semiconductor film formed using the oxide sintered material.

In order to improve the field effect mobility as well as the reliability under irradiation of light, the W content of the oxide sintered material is preferably more than or equal to 0.05 atom % and less than or equal to 3 atom %, and is more preferably less than or equal to 2 atom %. If the W content of the oxide sintered material is less than or equal to 0.01 atom %, reliability under irradiation of light becomes low in a semiconductor device including, as a channel layer, an oxide semiconductor film formed using the oxide sintered material. If the W content of the oxide sintered material is more than 5.0 atom %, field effect mobility becomes low in a semiconductor device including, as a channel layer, an oxide semiconductor film formed using a sputtering target including the oxide sintered material.

Thus, preferably, the range of the W content of the oxide sintered material is determined depending on the characteristics of the semiconductor device including, as a channel layer, the oxide semiconductor film formed using the oxide sintered material of the present embodiment, and the W content of the oxide semiconductor film normally indicates a value according to the W content of the oxide sintered material. However, the W content of the oxide semiconductor film does not necessarily need to be the same as the W content of the oxide sintered material.

In order to attain a small surface roughness of a sputtering target during sputtering, the W content of the oxide sintered material is more than 0.01 atom % and less than or equal to 5.0 atom %, is preferably more than 0.01 atom % and less than or equal to 3 atom %, is more preferably more than 0.01 atom % and less than or equal to 1 atom %, and is further preferably less than 0.5 atom %. If the W content of the oxide sintered material is less than or equal to 0.01 atom %, the apparent density of the oxide sintered material tends to be too low. If the W content of the oxide sintered material is more than 5.0 atom %, when such an oxide sintered material is applied to a sputtering target, the surface roughness of the sputtering target during sputtering becomes large, thus resulting in a large surface roughness of a formed oxide semiconductor film.

Since the W element has a large atomic weight to result in a low sputtering ratio, a crystal phase containing W is less likely to be etched than other phases during sputtering, and is therefore likely to provide protrusions in the target surface. When the W content of the oxide sintered material is low, the area ratio of the crystal phase containing W in the target surface becomes small, thereby reducing the protrusions during sputtering. Accordingly, the surface roughness can be small.

Generally, an oxide sintered material obtained by mixing indium oxide with tungsten oxide has a low apparent density. Although the apparent density can be increased by containing Zn and increasing contact points between W and Zn, a desired W content determined in consideration of the characteristics of the semiconductor device is small to fall within a range of more than 0.01 atom % and less than or equal to 5.0 atom %, so that it is preferable to increase the Zn content in order to realize an oxide sintered material having a higher apparent density. When the Zn content is less than 1.2 atom %, it tends to be difficult to obtain a sufficiently high apparent density. When the Zn content is more than or equal to 50 atom %, electric resistance of the oxide sintered material becomes high, with the result that it tends to be difficult to perform sputtering under application of DC voltage. The Zn content is preferably more than or equal to 11 atom % and is more preferably more than or equal to 15 atom %. Accordingly, an average aspect ratio of more than or equal to 1.5 is likely to be obtained in particles of a below-described third crystal phase. Moreover, when the Zn/W ratio is less than or equal to 1.0, it tends to be difficult to obtain a sufficiently high apparent density. In view of this, the Zn/W ratio is preferably more than or equal to 15. When the Zn/W ratio is more than or equal to 20000, electric resistance in the oxide sintered material becomes high, with the result that it tends to be difficult to perform sputtering under application of DC voltage. In view of this, the Zn/W ratio is preferably less than or equal to 100. The contents of In, Zn, and W in the oxide sintered material can be measured by ICP mass analysis.

The oxide sintered material of the present embodiment can exhibit a high apparent density even with a comparatively low sintering temperature, and can attain a reduced surface roughness of a sputtering target during sputtering when applied to the sputtering target. The oxide sintered material of the present embodiment can be used suitably as a sputtering target for forming an oxide semiconductor film (for example, an oxide semiconductor film serving as a channel layer) of a semiconductor device.

According to the oxide sintered material of the present embodiment, a semiconductor device having high field effect mobility as well as high reliability under irradiation of light can be obtained.

(3) Third Crystal Phase

The oxide sintered material of the present embodiment preferably includes a third crystal phase, which is a crystal phase different from the first crystal phase and contains zinc (Zn). The inclusion of the third crystal phase is advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering, and is also advantageous in improving field effect mobility as well as reliability under irradiation of light in a semiconductor device including, as a channel layer, an oxide semiconductor film formed using the oxide sintered material. The third crystal phase may be the same phase as the second crystal phase. The third crystal phase is a phase that can be included in a part of the oxide sintered material.

The third crystal phase is a crystal phase containing Zn, more typically, a phase having a Zn content (a content (atom %) of Zn relative to the total of In, W, and Zn) higher than that of the first crystal phase. The existence of the third crystal phase can be confirmed through the surface analysis using SEM-EDX performed when determining the high-content indium type crystal phase ratio, and the third crystal phase is represented by a crystal phase including the crystal particles of group A classified as a result of the surface analysis. The third crystal phase preferably has a Zn content of more than or equal to 50 atom %. In order to realize an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering, the Zn content of the third crystal phase is more preferably more than or equal to 60 atom %, and is further preferably more than or equal to 70 atom % The Zn content of the third crystal phase may be 100 atom %.

The third crystal phase is at least one crystal phase selected from a group consisting of: a below-described fourth crystal phase; a fifth crystal phase, which is a below-described zinc tungstate compound crystal phase; and a hexagonal wurtzite type crystal phase. The third crystal phase may be constituted of only one type of crystal phase or may include two or more types of crystal phases.

Preferably, the crystal particles included in the third crystal phase have an average major axis size of more than or equal to 3 μm and less than or equal to 50 μm, and have an average aspect ratio of more than or equal to 1.5 and less than or equal to 50. This is advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering, and is also advantageous in improving field effect mobility as well as reliability under irradiation of light in a semiconductor device including, as a channel layer, an oxide semiconductor film formed using the oxide sintered material.

The average major axis size and the average aspect ratio are determined as follows. When a reflection electron image is used for the SEM observation in the surface analysis employing SEM-EDX performed when determining the high-content indium type crystal phase ratio, group A representing the third crystal phase is observed in gray deeper than group B classified as the first crystal phase. The major axis length and minor axis length of each of the crystal particles included in the third crystal phase observed in the deeper gray in the reflection electron image captured in ×500 are measured to calculate an aspect ratio, which is a ratio (major axis length/minor axis length) of the major axis length to the minor axis length. The minor axis length is measured at a location ½ of the major axis length. It should be noted that the third crystal phase to be measured does not need to be a single crystal and may include particles of aggregated polycrystals, and a region of the independent third crystal phase surrounded by the first crystal phase is measured as one particle.

100 minor axis lengths and 100 major axis lengths from the third crystal phase are measured at random in a field of view of 170 μm×250 μm in the reflection electron image captured in ×500 in the SEM observation, and an average value of 20 major axis lengths from the third largest to twenty second largest major axis lengths is regarded as the average major axis size.

Similarly, 100 minor axis lengths and 100 major axis lengths from the third crystal phase are measured at random in the field of view of 170 μm: 250 μm in the reflection electron image captured in ×500 in the SEM observation so as to calculate an aspect ratio (major axis length/minor axis length) of each particle in the third crystal phase. Then, an average value of 20 aspect ratios from the third largest to twenty second aspect ratios is regarded as the average aspect ratio.

An average major axis size of more than or equal to 3 μm and less than or equal to 50 μm is advantageous in realizing an oxide sintered material that has a high apparent density and that attains a small surface roughness of a sputtering target during sputtering. When the average major axis size is smaller than 3 μm, the surface roughness of the sputtering target during sputtering is less likely to be small. When the average major axis size is larger than 50 μm, a sufficiently high apparent density tends to be less likely to be obtained and the surface roughness of the sputtering target during sputtering tends to be less likely to be small. The average major axis size is more preferably more than or equal to 10 μm and is further preferably more than or equal to 15 μm. Moreover, the average major axis size is more preferably less than or equal to 40 μm, and is further preferably less than or equal to 30 μm.

An average aspect ratio of more than or equal to 1.5 and less than or equal to 50 is advantageous in realizing an oxide sintered material that has a high apparent density and that attains a small surface roughness of a sputtering target during sputtering. When the average aspect ratio is less than 1.5, no sufficiently small surface roughness tends to be obtained. When the average aspect ratio is more than 50, no sufficiently high apparent density tends to be obtained. The average aspect ratio is more preferably more than or equal to 4, is further preferably more than or equal to 6, and is still more preferably more than or equal to 8. Moreover, the average aspect ratio is more preferably less than or equal to 40, and is further preferably less than or equal to 30.

The third crystal phase is preferably dispersed in the first crystal phase. This is advantageous in using the oxide sintered material of the present embodiment as a sputtering target.

In the sputtering method, DC voltage is employed for voltage applied to a sputtering target. In this case, the sputtering target is required to have electric conductivity. This is due to the following reason: when the electric resistance of the sputtering target is high, DC voltage cannot be applied, with the result that film formation (formation of an oxide semiconductor film) cannot be performed by the sputtering method.

When an oxide sintered material used as a sputtering target has a portion with a wide region having a high electric resistance, DC voltage is not applied to the region having a high electric resistance, with the result that the region may not be sputtered, disadvantageously. Alternatively, abnormal discharge referred to as “arcing” occurs in the region having a high electric resistance, with the result that film formation may not be performed normally, disadvantageously.

Since the third crystal phase has a higher electric resistance than that of the first crystal phase, the above-mentioned problem may occur if the third crystal phase exists in a wide region. In view of this, the third crystal phase is preferably dispersed in the first crystal phase as described above. The term “disperse” herein means that crystal particles having an average major axis size of more than or equal to 3 μm and less than or equal to 50 μm and having an average aspect ratio of more than or equal to 1.5 and less than or equal to 50 preferably exist in the form of individual crystal particles or in the form of aggregates each constituted of five or less such crystal particles at most. The dispersion state can be confirmed through a reflection electron image in the above-described ×500 SEM observation.

The third crystal phase is a crystal phase different from the first crystal phase and preferably includes a fourth crystal phase having a first diffraction peak at a location of more than 31.77 deg and less than 32.00 deg of 2θ in the X-ray diffraction. The inclusion of the fourth crystal phase is advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering, and is also advantageous in improving field effect mobility as well as reliability under irradiation of light in a semiconductor device including, as a channel layer, an oxide semiconductor film formed using the oxide sintered material. The fourth crystal phase may be the same phase as the second crystal phase. The fourth crystal phase is a phase that can be included in a part of the oxide sintered material.

In realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering the location of the second diffraction peak is preferably more than 31.8 deg and preferably less than or equal to 31.96 deg. The second diffraction peak observed at the location of more than 31.77 deg and less than 32.00 deg of 2θ in the X-ray diffraction means that plane spacing is more than 2.795 Å and less than 2.814 Å.

Existence of the fourth crystal phase can be confirmed through X-ray diffraction. For measurement conditions for the X-ray diffraction, the conditions indicated in “(2) Second Crystal Phase” above are employed. Although the fourth crystal phase is considered to be, for example, In₂O₃(ZnO)₅, the second diffraction peak indicated by the fourth crystal phase is generally located around 31.92 deg, which is at a low-angle side relative to the diffraction peak location of In₂O₃(ZnO)₅. Hence, it is not certain at present whether or not the fourth crystal phase is actually In₂O(ZnO)₅. Moreover, when the fourth crystal phase is actually In₂O₃(ZnO)₅, the fourth crystal phase is different from the second crystal phase.

In the oxide sintered material of the present embodiment, a ratio Ia/Ib of a peak intensity Ia of the first diffraction peak to a peak intensity Ib of the second diffraction peak is preferably more than or equal to 0.05 and less than or equal to 3. Ia/Ib of more than or equal to 0.05 and less than or equal to 3 is advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering, and is also advantageous in improving field effect mobility as well as reliability under irradiation of light in a semiconductor device including, as a channel layer, an oxide semiconductor film formed using the oxide sintered material.

When Ia/Ib is less than 0.05, the surface roughness of the sputtering target during sputtering does not tend to be small. In view of this, Ia/Ib is more preferably more than or equal to 0.1 and is further preferably more than or equal to 0.2. It is not easy to prepare an oxide sintered material having Ia/Ib of more than 3. In order to attain a small surface roughness of the sputtering target during sputtering, Ia/Ib is more preferably less than or equal to 2.

Peak intensities Ia and Ib in the X-ray diffraction are determined as follows. First, in a range of 20 of more than or equal to 32.15 deg and less than or equal to 32.90 deg, an average value lave of signal intensities I of the X-ray diffraction is calculated. Next, a signal intensity Ia′ of the first diffraction peak and a signal intensity Ib′ of the second diffraction peak are measured and peak intensity Ia of the first diffraction peak is determined from the following formula:

Ia=Ia′−Iave

Similarly, peak intensity Ib of the second diffraction peak is determined from the following formula.

Ib=Ib′−Iave

These calculations are intended to remove a background in the X-ray diffraction.

When there is no orientation in a sample, Ia/Ib indicates a value intrinsic to a material thereof; however, Ia/Ib may indicate a value different from the value intrinsic to the material thereof in the oxide sintered material of the present embodiment. In this case, when the second crystal phase having the first diffraction peak and the fourth crystal phase having the second diffraction peak are the same compound, this compound is considered to have an orientation. Moreover, when the second crystal phase having the first diffraction peak and the fourth crystal phase having the second diffraction peak are different compounds, it is considered that the second crystal phase and/or the fourth crystal phase have an orientation or Ia/Ib has a value reflecting a ratio of the second crystal phase and fourth crystal phase existing therein. Depending on a crystal orientation, the surface roughness of the sputtering target (oxide sintered material) during sputtering can be different. In the oxide sintered material of the present embodiment, Ia/Ib of more than or equal to 0.05 and less than or equal to 3 is advantageous in attaining a small surface roughness of the sputtering target during sputtering.

Moreover, the third crystal phase can include a fifth crystal phase, which is a crystal phase different from the first crystal phase and is a zinc tungstate compound crystal phase. The further inclusion of the fifth crystal phase is advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering, and is also advantageous in improving field effect mobility as well as reliability under irradiation of light in a semiconductor device including, as a channel layer, an oxide semiconductor film formed using the oxide sintered material. The fifth crystal phase may be the same phase as the second crystal phase or the fourth crystal phase. The fifth crystal phase is a phase that can be included in a part of the oxide sintered material.

In the present specification, the term “zinc tungstate compound crystal phase” is a crystal phase having Zn, W, and O as its main component. An example thereof is a ZnWO₄ type crystal phase. The term “ZnWO₄ type crystal phase” is a general term encompassing a ZnWO₄ crystal phase and a phase in which at least one of elements other than Zn and W is included in at least a part of the ZnWO₄ crystal phase and which has the same crystal structure as that of the ZnWO₄ crystal phase. The ZnWO₄ crystal phase is a zinc tungstate compound crystal phase having a crystal structure represented by a space group P12/c1(13) and having a crystal structure defined in 01-088-0251 of the JCPDS card. As long as the crystal structure is exhibited, oxygen may lack or a metal may be dissolved in a solid state to result in a change in lattice constant.

The existence of the fifth crystal phase can be confirmed by existence of a peak belonging to the “zinc tungstate compound crystal phase” in the X-ray diffraction. For example, the existence of the fifth crystal phase can be confirmed by existence of a peak belonging to the above-described ZnWO₄ type crystal phase. For measurement conditions for the X-ray diffraction, the conditions indicated in “(2) Second Crystal Phase” above are employed.

Moreover, the third crystal phase can further include a hexagonal wurtzite type crystal phase. The further inclusion of the hexagonal wurtzite type crystal phase is advantageous in realizing an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering, and is also advantageous in improving field effect mobility as well as reliability under irradiation of light in a semiconductor device including, as a channel layer, an oxide semiconductor film formed using the oxide sintered material. The hexagonal wurtzite type crystal phase may be the same phase as the fourth crystal phase. When the hexagonal wurtzite type crystal phase is the fourth crystal phase, the fourth crystal phase is different from the second crystal phase. The hexagonal wurtzite type crystal phase is a phase that can be included in a part of the oxide sintered material.

In the present specification, the term “hexagonal wurtzite type crystal phase” is a general term encompassing a hexagonal wurtzite crystal phase and a phase in which at least one of metallic elements other than Zn is included in at least a part of the hexagonal wurtzite crystal phase and which has the same crystal structure as that of the hexagonal wurtzite crystal phase. The hexagonal wurtzite crystal phase is one of crystal phases of zinc oxide (ZnO), and is a crystal structure represented by a space group P63mc and a space group No. 186 and defined in 01-079-0207 of the JCPDS card.

The existence of the hexagonal wurtzite type crystal phase can be confirmed by existence of a peak belonging to the “hexagonal wurtzite type crystal phase” in the X-ray diffraction. For example, the existence of the hexagonal wurtzite type crystal phase can be confirmed by existence of a peak belonging to the above-described zinc oxide. For measurement conditions for the X-ray diffraction, the conditions indicated in “(2) Second Crystal Phase” above are employed.

The hexagonal wurtzite type crystal phase includes ZnO as its main component, and W and/or In may be substitutionally and/or interstitially dissolved in a solid state in at least a part of the hexagonal wurtzite type crystal phase. In order to confirm that they are dissolved in a solid state, a method employing X-ray diffraction, SEM-EDX, or TEM-EDX is applicable as with the above-described method of confirming whether or not “W and/or Zn are dissolved in a solid state in at least a part of the first crystal phase”.

It should be noted that the oxide sintered material of the present embodiment may further contain zirconium (Zr). The content of zirconium (Zr) is more than or equal to 1×10¹⁷ atms/cm³ and less than or equal to 1×10²⁰ atms/cm³, for example.

Zr is an element that can be mixed in the process of producing the oxide sintered material, but does not hinder attainment of the high apparent density of the oxide sintered material and attainment of the small surface roughness of the sputtering target during sputtering. The existence and content of Zr can be confirmed by a secondary ion mass spectrometer.

(5) Application of Oxide Sintered Material to Sputtering Target

The oxide sintered material of the present embodiment can be suitably used as a sputtering target. The term “sputtering target” refers to a source material in a sputtering method. The sputtering method refers to a method of forming a film composed of atoms from a sputtering target disposed to face a substrate in a film formation chamber in the following manner: voltage is applied to the sputtering target and a surface of the target is sputtered by noble gas ions to release atoms of the target and accordingly deposit them on the substrate.

Intrinsically, the elements of the sputtering target are separated by the noble gas ions in the atomic level; however, if there is a protrusion in the surface, fine particles may jump out of the protrusion and be mixed into the film, or due to concentration of electric field in the protrusion, the number of atoms jumping out at that portion is increased to thereby change the film thickness in the in-plane direction. Hence, when the surface of the sputtering target is rough, the thin film formed therefrom may become rough.

Moreover, a low apparent density means that there are a multiplicity of submicron-sized holes (pores) in the sputtering target. When there is a pore, the same phenomenon as that for the above-described protrusion occurs at a peripheral portion surrounding the pore, with the result that the formed thin film may also become rough.

In order to further improve field effect mobility and more improve reliability under irradiation of light in a semiconductor device including an oxide semiconductor film formed by the sputtering method using an oxide sintered material as a sputtering target, it has been found that it is desirable to attain a small surface roughness of the formed oxide semiconductor film.

The oxide semiconductor film forms an interface with each of various films such as a gate insulating film, an etch stopper layer, a source electrode, a drain electrode, and a passivation film. When there is irregularity in the interface, transfer of electrons is hindered, thus presumably resulting in decreased field effect mobility. Various defect levels are likely to be generated in the above-described interface. The area of the interface becomes larger as the surface roughness becomes larger. Accordingly, the number of defects is also increased, with the result that excitation and dissipation of carriers are likely to occur under irradiation of light. This presumably leads to deteriorated reliability under irradiation of light.

When the oxide sintered material of the present embodiment is applied to a sputtering target, the surface roughness of the sputtering target during sputtering can be made small, with the result that the surface roughness of the formed oxide semiconductor film can be small.

Moreover, when the surface roughness of the formed oxide semiconductor film is large, various films formed thereon, such as a gate insulating film, an etch stopper layer, a source electrode, a drain electrode, and a passivation film, tend to be detached. This is often due to the following reason: the above-described upper layers (such as the gate insulating film, the etch stopper layer, the source electrode, the drain electrode, and the passivation film) are broken down by occurrence of stress concentration at a protrusion or recess in the film. By applying the oxide sintered material of the present embodiment to a sputtering target, the surface roughness of the sputtering target during sputtering can be made small, whereby the above-described detachment can be suppressed.

Since the oxide sintered material of the present embodiment particularly includes the predetermined second crystal phase and has the appropriate W content, Zn content, and Zn/W ratio, the oxide sintered material of the present embodiment is an oxide sintered material conforming to the above-described request to attain a small surface roughness of a sputtering target during sputtering.

Second Embodiment: Method of Producing Oxide Sintered Material

One of methods of producing an oxide sintered material according to the present embodiment is a method of producing the oxide sintered material according to the first embodiment, and includes the steps of: preparing a primary mixture of a zinc oxide powder and a tungsten oxide powder; forming a calcinated powder by heating the primary mixture; preparing a secondary mixture of source powders including the calcinated powder; forming a molded body by molding the secondary mixture; and forming the oxide sintered material by sintering the molded body. The step of forming the calcinated powder includes forming a powder of a complex oxide including Zn and W as the calcinated powder by heating the primary mixture at a temperature of more than or equal to 550° C. and less than 1200° C. in an oxygen-containing atmosphere.

According to the production method above, since the step of forming the calcinated powder includes forming the complex oxide powder including Zn and W as the calcinated powder by heating the primary mixture of the zinc oxide powder and the tungsten oxide powder at a temperature of more than or equal to 550° C. and less than 1200° C. in the oxygen-containing atmosphere, it is possible to obtain an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature, that attains a small surface roughness of a sputtering target during sputtering, and that can be used suitably as the sputtering target. Regarding the complex oxide, oxygen may lack or a metal may be substituted.

When the heating temperature is less than 550° C., the complex oxide powder including Zn and W is not obtained. When the heating temperature is more than or equal to 1200° C., the complex oxide powder including Zn and W is decomposed and scattered or the particle size of the complex oxide powder tends to be too large to such an extent that it is not suitable for use.

Moreover, since the complex oxide powder including Zn and W as the calcinated powder is formed by the heating, the field effect mobility as well as the reliability under irradiation of light can be more effectively improved in the semiconductor device including, as a channel layer, the oxide semiconductor film formed using the sputtering target including the obtained oxide sintered material.

The complex oxide including Zn and W preferably includes a ZnWO₄ type crystal phase. Accordingly, the apparent density of the oxide sintered material can be improved more effectively and the surface roughness of the sputtering target during sputtering can be more effectively made small. The ZnWO₄ type crystal phase is a zinc tungstate compound crystal phase having a crystal structure represented by a space group P12/c1(13) and having a crystal structure defined in 01-088-0251 of the JCPDS card. As long as the crystal structure is exhibited, oxygen may lack or a metal may be dissolved in a solid state to result in a change in lattice constant. The ZnWO₄ type crystal phase is identified by X-ray diffraction measurement.

Moreover, another one of the methods of producing the oxide sintered material according to the present embodiment is a method of producing the oxide sintered material according to the first embodiment, and includes the steps of: preparing a primary mixture of an indium oxide powder and a tungsten oxide powder, forming a calcinated powder by heating the primary mixture; preparing a secondary mixture of source powders including the calcinated powder; forming a molded body by molding the secondary mixture; and forming an oxide sintered material by sintering the molded body. The step of forming the calcinated powder includes forming a powder of a complex oxide including In and W as the calcinated powder by heating the primary mixture at a temperature of more than or equal to 700° C. and less than 1400° C. in an oxygen-containing atmosphere.

According to the production method above, since the step of forming the calcinated powder includes forming the complex oxide powder including In and W as the calcinated powder by heating the primary mixture of the indium oxide powder and the tungsten oxide powder at a temperature of more than or equal to 700° C. and less than 1400° C. in the oxygen-containing atmosphere, it is possible to obtain an oxide sintered material that has a high apparent density even with a comparatively low sintering temperature, that attains a small surface roughness of a sputtering target during sputtering, and that can be used suitably as the sputtering target. Regarding the complex oxide, oxygen may lack or a metal may be substituted.

When the heating temperature is less than 700° C., the complex oxide powder including In and W is not obtained. When the heating temperature is more than or equal to 1400° C., the complex oxide powder including In and W is decomposed and scattered or the particle size of the complex oxide powder tends to be too large to such an extent that it is not suitable for use.

Moreover, since the complex oxide powder including In and W as the calcinated powder is formed by the heating, the field effect mobility as well as the reliability under irradiation of light can be more effectively improved in the semiconductor device including, as a channel layer, the oxide semiconductor film formed using the sputtering target including the obtained oxide sintered material.

The complex oxide including In and W preferably includes an In₆WO₁₂ type crystal phase. Accordingly, the apparent density of the oxide sintered material can be improved more effectively and the surface roughness of the sputtering target during sputtering can be more effectively made small. The In₆WO₁₂ crystal phase is an indium tungstate compound crystal phase having a trigonal crystal structure and having a crystal structure defined in 01-074-1410 of the JCPDS card. As long as the crystal structure is exhibited, oxygen may lack or a metal may be dissolved in a solid state to result in a change in lattice constant. It should be noted that since an indium tungstate compound crystal phase disclosed in Japanese Patent Laying-Open No. 2004-091265 is an InW₃O₉ crystal phase, has a hexagonal crystal structure, and has a crystal structure defined in 33-627 of the JCPDS card, the crystal structure thereof is different from that of the In₆WO₁₂ crystal phase. The In₆WO₁₂ type crystal phase is identified by X-ray diffraction measurement.

It has been known that W hinders sintering of indium oxide, which accordingly hinders achievement of a high apparent density of the oxide sintered material. However, according to the production method of the present invention, an oxide sintered material having a high apparent density can be obtained even with a low sintering temperature by using the complex oxide powder including In and W, and/or the complex oxide powder including Zn and W, and/or the complex oxide powder including In and Zn. Moreover, the obtained oxide sintered material has such a feature as to attain a small surface roughness of a sputtering target during sputtering.

In order to increase the apparent density of the oxide sintered material including In, W, and Zn, it is effective that the complex oxide including Zn and W having low melting points is present during the sintering. To attain this, it is preferable to increase contact points between the tungsten oxide and the zinc oxide during the sintering and to form the complex oxide including Zn and W. Therefore, in order to obtain a high apparent density even with a low sintering temperature or attain a small surface roughness of a sputtering target during sputtering, it is preferable to employ: a method of using, for the production process, the complex oxide powder including Zn and W synthesized in advance; and/or a method of increasing the contact points with Zn by using the complex oxide powder including In and W synthesized in advance. These methods may be used solely or in combination. For example, both the method of using, for the production process, the complex oxide powder including Zn and W synthesized in advance, and the method of using the complex oxide powder including indium and tungsten synthesized in advance may be used. In order to realize an oxide sintered material that has a high apparent density with a low sintering temperature and that attains a small surface roughness of a sputtering target during sputtering, it is more preferable to use at least the method of using, for the production process, the complex oxide powder including Zn and W synthesized in advance.

The tungsten oxide powder used for the production of the oxide sintered material preferably includes at least one selected from a group consisting of a WO₃ crystal phase, a WO₂ crystal phase, and a WO_(2.72) crystal phase. Accordingly, the apparent density of the oxide sintered material can be improved more effectively and the surface roughness of the sputtering target during sputtering can be more effectively made small. Moreover, this is advantageous in improving field effect mobility as well as reliability under irradiation of light in a semiconductor device including the oxide semiconductor film as a channel layer, for example.

Moreover, the tungsten oxide powder preferably has a median particle size d50 of more than or equal to 0.1 μm and less than or equal to 4 μm, more preferably, more than or equal to 0.2 μm and less than or equal to 2 μm, and further preferably more than or equal to 0.3 μm and less than or equal to 1.5 μm. Accordingly, the apparent density of the oxide sintered material can be improved more effectively and the surface roughness of the sputtering target during sputtering can be more effectively made small. Median particle size d50 is determined by BET specific surface area measurement. When median particle size d50 is less than 0.1 μm, it is difficult to handle the powder, with the result that it tends to be difficult to uniformly mix the zinc oxide powder with the tungsten oxide powder or uniformly mix the indium oxide powder with the tungsten oxide powder.

Median particle size d50 of more than 4 μm leads to a large particle size of the complex oxide powder including Zn and W obtained by heating at a temperature of more than or equal to 550° C. and less than 1200° C. in the oxygen-containing atmosphere after mixing with the zinc oxide powder, with the result that it tends to be difficult to more effectively improve the apparent density of the oxide sintered material and to more effectively attain a small surface roughness of a sputtering target during sputtering. Similarly, median particle size d50 of more than 4 μm leads to a large particle size of the complex oxide powder including In and W obtained by heating at a temperature of more than or equal to 700° C. and less than 1400° C. in the oxygen-containing atmosphere after mixing with the indium oxide powder, with the result that it tends to be difficult to more effectively improve the apparent density of the oxide sintered material and more effectively attain a small surface roughness of a sputtering target during sputtering

Although the method of producing the oxide sintered material according to the present embodiment should not be particularly limited, the method of producing the oxide sintered material according to the present embodiment includes, for example, the following steps in order to form the oxide sintered material of the first embodiment efficiently.

(1) Step of Preparing Source Powders

As the source powders of the oxide sintered material, oxide powders of metallic elements to be included in the oxide sintered material are prepared, such as an indium oxide powder (for example, In₂O₃ powder), a tungsten oxide powder (for example, WO₃ powder, WO_(2.72) powder, or WO₂ powder), and a zinc oxide powder (for example, ZnO powder). In order to improve the field effect mobility as well as the reliability under irradiation of light in the semiconductor device, it is preferable to use, as the tungsten oxide powder of the source materials, not only the WO₃ powder but also a powder having a chemical composition lacking oxygen as compared with the WO₃ powder, such as the WO_(2.72) powder or the WO₂ powder. In view of this, at least one of the WO_(2.72) powder and the WO₂ powder is more preferably used as at least a part of the tungsten oxide powder. The source powders preferably have a high purity of more than or equal to 99.9 mass % in order to prevent unintended introduction of a metallic element and Si into the oxide sintered material and to obtain a stable physical property.

As described above, median particle size d50 of the tungsten oxide powder is preferably more than or equal to 0.1 μm and less than or equal to 4 μm in order to more effectively improve the apparent density of the oxide sintered material and more effectively attain a small surface roughness of a sputtering target during sputtering.

(2) Step of Preparing Primary Mixture

(2-1) Step of Preparing Primary Mixture of Zinc Oxide Powder and Tungsten Oxide Powder

The zinc oxide powder and tungsten oxide powder of the source powders are mixed (or pulverized and mixed). In doing so, if it is desired to obtain the ZnWO₄ type crystal phase as the crystal phase of the oxide sintered material, the tungsten oxide powder and the zinc oxide powder are mixed at a molar ratio of 1:1. On the other hand, if it is desired to obtain the Zn₂W₃O₈ type crystal phase, the tungsten oxide powder and the zinc oxide powder are mixed at a molar ratio of 3:2. As described above, in order to more effectively improve the apparent density of the oxide sintered material, attain a small surface roughness of a sputtering target during sputtering, and improve the field effect mobility as well as the reliability under irradiation of light in the semiconductor device, the oxide sintered material preferably includes the ZnWO₄ type phase. A method of mixing the tungsten oxide powder with the zinc oxide powder should not be particularly limited and may be a dry type method or a wet type method. Specifically, the tungsten oxide powder and the zinc oxide powder are pulverized and mixed using a ball mill, a planetary ball mill, a bead mill, or the like. In this way, the primary mixture of the source powders is obtained. For drying of the mixture obtained using the wet type pulverization and mixing method, a drying method such as natural drying or a spray dryer can be used.

(2-2) Step of Preparing Primary Mixture of Indium Oxide Powder and Tungsten Oxide Powder

The indium oxide powder and tungsten oxide powder of the source powders are mixed (or pulverized and mixed). In doing so, if it is desired to obtain the In₆WO₁₂ type crystal phase as the crystal phase of the oxide sintered material, the tungsten oxide powder and the indium oxide powder are mixed at a molar ratio of 1:3. A method of mixing the tungsten oxide powder with the indium oxide powder should not be particularly limited, and may be the dry type method or the wet type method. Specifically, the tungsten oxide powder and the zinc oxide powder are pulverized and mixed using a ball mill, a planetary ball mill, a bead mill, or the like In this way, the primary mixture of the source powders is obtained. For drying of the mixture obtained using the wet type pulverization and mixing method, a drying method such as natural drying or a spray dryer can be used.

(3) Step of Forming Calcinated Powder

(3-1) Step of Forming Calcinated Powder of Tungstate Zinc Oxide

The obtained primary mixture is heated (calcinated) to form the calcinated powder (complex oxide powder including Zn and W). The calcination temperature of the primary mixture is preferably less than 1200° C. to prevent the particle size of the calcinated powder from being too large and accordingly resulting in a decreased apparent density of the oxide sintered material and to prevent the surface roughness of the sputtering target during sputtering from being large. In order to obtain the complex oxide powder including Zn and W as a calcinated product or in order to obtain the ZnWO₄ type crystal phase, the calcination temperature of the primary mixture is preferably more than or equal to 550° C. The calcination temperature of the primary mixture is more preferably more than or equal to 550° C. and less than 1000° C., and is further preferably more than or equal to 550° C. and less than or equal to 900° C. The calcination temperature is preferably lower as long as the crystal phase is formed at the calcination temperature, since the particle size of the calcinated powder can be made as small as possible. In this way, the calcinated powder including the ZnWO₄ type crystal phase can be obtained. The calcination atmosphere may be any atmosphere as long as the atmosphere includes oxygen. However, it is preferable to employ: an air atmosphere having an atmospheric pressure or having a pressure higher than that of the atmospheric air; or an oxygen-nitrogen mixture atmosphere having an atmospheric pressure or including more than or equal to 25 volume % of oxygen having a pressure higher than that of the atmospheric air. For high productivity, the air atmosphere having an atmospheric pressure or a pressure therearound is more preferable.

(3-2) Step of Forming Calcinated Powder of Indium Tungstate Oxide

The obtained primary mixture is heated (calcinated) to form the calcinated powder (complex oxide powder including In and W). The calcination temperature of the primary mixture is preferably less than 1400° C. to prevent the particle size of the calcinated product from being too large and accordingly resulting in a decreased apparent density of the oxide sintered material and to prevent the surface roughness of the sputtering target during sputtering from being large. In order to obtain the complex oxide powder including In and W as the calcinated product or obtain the In₆WO₁₂ type crystal phase, the calcination temperature of the primary mixture is preferably more than or equal to 700° C. More preferably, the calcination temperature of the primary mixture is more than or equal to 800° C. and less than 1300° C. The calcination temperature is preferably lower as long as the crystal phase is formed at the calcination temperature, since the particle size of the calcinated powder can be made as small as possible. In this way, the calcinated powder including the In₆WO₁₂ type crystal phase can be obtained. The calcination atmosphere may be any atmosphere as long as the atmosphere includes oxygen. However, it is preferable to employ: an air atmosphere having an atmospheric pressure or having a pressure higher than that of the atmospheric air; or an oxygen-nitrogen mixture atmosphere having an atmospheric pressure or including more than or equal to 25 volume % of oxygen having a pressure higher than that of the atmospheric air. For high productivity, the air atmosphere having an atmospheric pressure or a pressure therearound is more preferable.

(4) Step of Preparing Secondary Mixture of Source Powders Including Calcinated Powder

Next, in the same manner as in the preparation of the primary mixture, the obtained calcinated powder is mixed (or pulverized and mixed) with the remainder (the indium oxide powder (for example, In₂O₃ powder) or the zinc oxide powder (for example, ZnO powder)) of the source powders. In this way, the secondary mixture of the source powders is obtained. The tungsten oxide preferably exists as a complex oxide as a result of the calcination step.

(5) Step of Forming Molded Body by Molding Secondary Mixture

Next, the obtained secondary mixture is molded. Although a method of molding the secondary mixture should not be particularly limited, it is preferable to employ an uniaxial pressing method, a CIP (Cold Isostatic Pressing) method, a casting method, or the like in order to increase the apparent density of the oxide sintered material.

(6) Step of Forming Oxide Sintered Material by Sintering Molded Body

Next, the obtained molded body is sintered to form the oxide sintered material. In doing so, for productivity, it is preferable not to employ a hot-press sintering method. Although the sintering temperature for the molded body should not be particularly limited, the sintering temperature is preferably more than or equal to 900° C. and less than 1200° C. in order to obtain an oxide sintered material that has an apparent density of more than 6.4 g/cm³ and that attains a small surface roughness of a sputtering target during sputtering. Although the sintering atmosphere also should not be particularly limited, the sintering atmosphere is preferably an air atmosphere having an atmospheric pressure or a pressure therearound in order to prevent the particle size of the crystal of the oxide sintered material from being large and obtain an oxide sintered material that attains a small surface roughness of a sputtering target during sputtering.

Third Embodiment: Sputtering Target

The sputtering target according to the present embodiment includes the oxide sintered material of the first embodiment. Hence, the sputtering target according to the present embodiment can be used suitably to form, by the sputtering method, an oxide semiconductor film of a semiconductor device having high field effect mobility as well as high reliability under irradiation of light.

The sputtering target according to the present embodiment preferably includes the oxide sintered material of the first embodiment and is more preferably composed of the oxide sintered material of the first embodiment such that the sputtering target can be used suitably to form, by the sputtering method, an oxide semiconductor film of a semiconductor device having high field effect mobility as well as high reliability under irradiation of light.

Fourth Embodiment: Semiconductor Device and Method of Producing Semiconductor Device

With reference to FIG. 1A and FIG. 1B, a semiconductor device 10 according to the present embodiment includes an oxide semiconductor film 14 formed using the oxide sintered material of the first embodiment or formed by the sputtering method using the sputtering target of the third embodiment. Since the semiconductor device according to the present embodiment includes such an oxide semiconductor film 14, the semiconductor device according to the present embodiment can have characteristics such as high field effect mobility as well as high reliability under irradiation of light.

Although semiconductor device 10 according to the present embodiment should not be particularly limited, semiconductor device 10 according to the present embodiment is preferably a TFT (thin film transistor) because it has high field effect mobility as well as high reliability under irradiation of light, for example. Since oxide semiconductor film 14 included in the TFT has high field effect mobility as well as high reliability under irradiation of light, oxide semiconductor film 14 preferably serves as a channel layer.

In semiconductor device 10 according to the present embodiment, the W content of oxide semiconductor film 14 is preferably more than 0.01 atom % and less than or equal to 5.0 atom %, the Zn content of oxide semiconductor film 14 is preferably more than or equal to 1.2 atom % and less than 50 atom %, and the Zn/W ratio of oxide semiconductor film 14 is preferably more than 1.0 and less than 20000. Accordingly, the field effect mobility as well as the reliability under irradiation of light can be improved in semiconductor device 10.

In order to improve the field effect mobility as well as the reliability under irradiation of light, the W content of oxide semiconductor film 14 is more preferably more than or equal to 0.05 atom % and less than or equal to 3 atom %, and is further preferably less than or equal to 2 atom % When the W content of oxide semiconductor film 14 is less than or equal to 0.01 atom %, the reliability under irradiation of light tends to be low in the semiconductor device including such an oxide semiconductor film 14 as a channel layer. When the W content of oxide semiconductor film 14 is more than 5.0 atom %, the field effect mobility tends to become low in the semiconductor device including such an oxide semiconductor film as a channel layer.

In order to attain a small surface roughness of oxide semiconductor film 14, the W content of oxide semiconductor film 14 is more than 0.01 atom % and less than or equal to 5.0 atom %, is preferably more than 0.01 atom % and less than or equal to 3 atom %, is more preferably more than 0.01 atom % and less than or equal to 1 atom %, and is further preferably less than 0.5 atom %. Since the W content falls within the above-described range, oxide semiconductor film 14 having a small surface roughness is more likely to be obtained.

When the Zn content of oxide semiconductor film 14 is more than or equal to 1.2 atom % and less than 50 atom % and the Zn/W ratio of oxide semiconductor film 14 is more than 1.0 and less than 20000, the field effect mobility as well as the reliability under irradiation of light can be increased in the semiconductor device including such an oxide semiconductor film 14 as a channel layer

In order to improve the field effect mobility as well as the reliability under irradiation of light, the Zn content of oxide semiconductor film 14 is more preferably more than 3 atom % and less than or equal to 40 atom %, is further preferably more than or equal to 5 atom % and less than 20 atom %, is still more preferably more than or equal to 11 atom %, and is particularly preferably more than or equal to 15 atom %.

When the Zn content of oxide semiconductor film 14 is less than 1.2 atom %, the reliability under irradiation of light tends to become low in the semiconductor device including such an oxide semiconductor film 14 as a channel layer. When the Zn content of oxide semiconductor film 14 is more than or equal to 50 atom %, the field effect mobility tends to be low in the semiconductor device including such an oxide semiconductor film 14 as a channel layer.

When the Zn/W ratio in oxide semiconductor film 14 is less than or equal to 1.0, the reliability under irradiation of light tends to be low in the semiconductor device including such an oxide semiconductor film 14 as a channel layer. The Zn/W ratio is more preferably more than or equal to 3.0, and is further preferably more than or equal to 5.0. When the Zn/W ratio is more than or equal to 20000 in oxide semiconductor film 14, the field effect mobility tends to be low in the semiconductor device including such an oxide semiconductor film 14 as a channel layer. The Zn/W ratio is more preferably less than 100.

The chemical composition of oxide semiconductor film 14, i.e., the respective contents of the elements, are measured by RBS (Rutherford Backscattering Spectrometry). Based on the result of measurement, the W content, the Zn content, and the Zn/W ratio are calculated. If the analysis with RBS cannot be performed, they are measured through TEM-EDX (Transmission Electron Microscope with Energy Dispersive X-Ray Fluorescent Emission Spectrometer). The measurement with RBS is desirable in view of precision in measuring the chemical composition. If the TEM-EDX is used, as samples for drawing a calibration curve, at least three or more oxide semiconductor films are first prepared each of which is composed of In, W, Zn, and O, has a composition close to that of the oxide semiconductor film to be measured, and can be analyzed by RBS. Next, the respective contents of In, W, and Zn in each of these samples are measured by RBS and the respective contents of In, W, and Zn in each of these samples are measured by TEM-EDX. Based on these measured values, a calibration curve is drawn to indicate a relation between the measured values of the contents of In, W, and Zn by TEM-EDX and the measured values of the contents of In, W, and Zn by RBS. Then, the respective contents of In, W, and Zn in the oxide semiconductor film to be measured are measured by TEM-EDX, and the resulting measured values are converted into measured values of the respective contents of In, W, and Zn by RBS based on the calibration curve. The converted values represent the respective contents of In, W and Zn in the measured oxide semiconductor film.

Oxide semiconductor 14 may further contain zirconium (Zr). The content of zirconium (Zr) is more than or equal to 1×10¹⁷ atms/cm³ and less than or equal to 1×10²⁰ atms/cm³, for example. Zr is an element that can be introduced in the production process for the oxide sintered material, and can be introduced into oxide semiconductor film 14 formed using this oxide sintered material as a source material; however, existence of Zr does not hinder high field effect mobility as well as high reliability under irradiation of light. The existence and content of zirconium can be confirmed by a secondary ion mass spectrometer.

Oxide semiconductor film 14 is preferably composed of at least one of a nano crystal oxide and an amorphous oxide because high field effect mobility as well as high reliability under irradiation of light can be achieved in a semiconductor device (for example, TFT) including such an oxide semiconductor film 14 as a channel layer.

In the present specification, the term “nano crystal oxide” refers to an oxide for which no peak resulting from crystal is observed and only a broad peak called “halo” appearing at the low angle side is observed in an X-ray diffraction measurement under below-described conditions, and for which a ring-like pattern is observed when performing transmission electron beam diffraction measurement in a minute region under below-described conditions using a transmission electron microscope. The term “ring-like pattern” encompasses a case where spots are gathered to form a ring-like pattern.

Moreover, in the present specification, the term “amorphous oxide” refers to an oxide for which no peak resulting from crystal is observed and only a broad peak called “halo” appearing at the low angle side is observed in the X-ray diffraction measurement under below-described conditions, and for which the unclear pattern called “halo” is also observed even when performing transmission electron beam diffraction measurement in a minute region under the below-described conditions using a transmission electron microscope.

(X-Ray Diffraction Measurement Conditions)

Measurement method: In-plane method (slit collimation method);

X-ray generator: anticathode Cu, output 50 kV 300 mA;

Detector: scintillation counter;

Incidence portion: slit collimation:

Soller slit: incidence side vertical divergence angle of 0.48°, light receiving side vertical divergence angle of 0.41°; Slit: incidence side S1 = 1 mm * 10 mm, light receiving side S2 = 0.2 mm * 10 mm; Scanning scanning axis 2θχ/ϕ; condition: Scanning step measurement, scanning range of 10° to 80°, step mode: width of 0.1°; step time: 8 sec.

(Transmission Electron Beam Diffraction Measurement Conditions)

Measurement Method: Microscopic Electron Beam Diffraction Method,

Acceleration voltage: 200 kV,

Beam diameter: the same as or equivalent to the film thickness of the oxide semiconductor film to be measured

If oxide semiconductor film 14 is composed of the nano crystal oxide, the ring-like pattern is observed as described above and no spot-like pattern is observed when performing transmission electron beam diffraction measurement in the minute region under the above conditions. On the other hand, an oxide semiconductor film disclosed in, for example, Japanese Patent No. 5172918 includes crystal oriented toward the c axis in a direction perpendicular to the surface of the film. When the nano crystal in the minute region is thus oriented in a certain direction, a spot-like pattern is observed. When oxide semiconductor film 14 is composed of the nano crystal oxide, the nano crystal is of non-orientation or has a random orientation, i.e., is not oriented toward the surface of the film when at least observing a plane (film cross section) perpendicular to the plane of the film. That is, the crystal axis thereof is not oriented in the film thickness direction.

Since oxide semiconductor film 14 is composed of the nano crystal oxide or the amorphous oxide, a semiconductor device including such an oxide semiconductor film 14 as a channel layer can achieve high field effect mobility. In order to improve field effect mobility, oxide semiconductor film 14 is more preferably composed of the amorphous oxide. The film thickness of oxide semiconductor film 14 is more than or equal to 2 nm and less than or equal to 60 nm, for example.

In the semiconductor device of the present embodiment, oxide semiconductor film 14 preferably has an electrical resistivity of more than or equal to 10⁻¹ Ωcm. A multiplicity of transparent conductive films employing indium oxide have been examined thus far, and an electrical resistivity of less than 10⁻¹ Ωcm is required for applications of such transparent conductive films. On the other hand, the oxide semiconductor film included in the semiconductor device of the present embodiment preferably has an electrical resistivity of more than or equal to 10⁻¹ Ωcm, whereby the oxide semiconductor film can be used suitably as a channel layer of the semiconductor device. When the electrical resistivity is less than 10⁻¹ Ωcm, it is difficult to use it as a channel layer of a semiconductor device.

Oxide semiconductor film 14 can be obtained by a production method including a step of forming a film through the sputtering method. The meaning of the sputtering method is defined as described above. As a method of forming the oxide semiconductor film, not only the sputtering method but also a pulse laser vapor deposition (PLD) method, a heating deposition method, and the like have been proposed; however, in view of productivity, the sputtering method is preferably used.

As the sputtering method, a magnetron sputtering method, a facing target magnetron sputtering method, or the like can be used. As an atmospheric gas during the sputtering, Ar gas, Kr gas, and Xe gas can be used, and may be mixed with and used together with oxygen gas.

Moreover, oxide semiconductor film 14 can be obtained by heating after forming the film by the sputtering method or can be obtained by heating while forming the film by the sputtering method. Accordingly, an oxide semiconductor film composed of the nano crystal oxide or the amorphous oxide can be readily obtained. Moreover, the oxide semiconductor film obtained by this method is advantageous in improving field effect mobility as well as reliability under irradiation of light in a semiconductor device (for example, TFT) including this oxide semiconductor film as a channel layer.

The heating performed while forming the film by the sputtering method can be performed by heating the substrate during the formation of the film. The substrate temperature is preferably more than or equal to 100° C. and less than or equal to 250° C. The heating time corresponds to the film formation time, and the film formation time can be, for example, about 10 seconds to 10 minutes although the film formation time depends on the film thickness of oxide semiconductor film 14 to be formed.

Likewise, the heating performed after forming the film by the sputtering method can be performed by heating the substrate. In order to obtain high reliability under irradiation of light, heating is preferably performed after forming the film by the sputtering method. In this case, the heating may be performed immediately after forming oxide semiconductor film 14, or may be performed after forming a source electrode, a drain electrode, an etch stopper layer (ES layer), a passivation layer, or the like. In order to obtain high reliability under irradiation of light, it is more preferable to perform heating after forming the etch stopper layer.

When performing heating after forming oxide semiconductor film 14, the substrate temperature is preferably more than or equal to 100° C. and less than or equal to 500° C. The heating may be performed in a various types of atmospheres such as atmospheric air, nitrogen gas, nitrogen gas-oxygen gas, Ar gas, Ar-oxygen gas, water-vapor-containing atmospheric air, and water-vapor-containing nitrogen. A pressure of the atmosphere can be an atmospheric pressure, a reduced pressure (for example, less than 0.1 Pa), or an increased pressure (for example, 0.1 Pa to 9 MPa), but is preferably the atmospheric pressure. The heating time can be, for example, about 3 minutes to 2 hours, and is preferably about 10 minutes to 90 minutes.

FIG. 1A, FIG. 1B, FIG. 2, and FIG. 3 are schematic views showing some exemplary semiconductor devices (TFT) according to the present embodiment. A semiconductor device 10 shown in FIG. 1A and FIG. 1B includes: a substrate 11; a gate electrode 12 disposed on substrate 11; a gate insulating film 13 disposed as an insulating layer on gate electrode 12; oxide semiconductor film 14 disposed as a channel layer on gate insulating film 13; and a source electrode 15 and a drain electrode 16 disposed on oxide semiconductor film 14 not in contact with each other.

A semiconductor device 20 shown in FIG. 2 has the same configuration as that of semiconductor device 10 shown in FIG. 1A and FIG. 1B except that semiconductor device 20 further includes: an etch stopper layer 17 disposed on gate insulating film 13 and oxide semiconductor film 14 and provided with a contact hole; and a passivation film 18 disposed on etch stopper layer 17, source electrode 15, and drain electrode 16. In semiconductor device 20 shown in FIG. 2, passivation film 18 can be omitted as in semiconductor device 10 shown in FIG. 1A and FIG. 1B. A semiconductor device 30 shown in FIG. 3 has the same configuration as semiconductor device 10 shown in FIG. 1A and FIG. 1B except that semiconductor device 30 further includes a passivation film 18 disposed on gate insulating film 13, source electrode 15, and drain electrode 16.

Each of the semiconductor devices according to the present embodiment includes oxide semiconductor film 14 described above, and preferably further includes a layer (hereinafter, also referred to as “amorphous adjacent layer”), which is disposed in contact with at least a portion of oxide semiconductor film 14 and which is an amorphous layer. According to the semiconductor device including the amorphous adjacent layer, high field effect mobility can be held and high reliability under irradiation of light can be realized when oxide semiconductor film 14 can be maintained to be composed of the amorphous oxide even if the temperature in the above-described heating is high. Examples of the amorphous adjacent layer include gate insulating film 13, passivation layer 18, and etch stopper layer 17.

The amorphous adjacent layer may be a layer formed in contact with oxide semiconductor film 14 as a layer (lower layer) lying below oxide semiconductor film 14, or may be an upper layer formed on/above and in contact with oxide semiconductor film 14. Moreover, the semiconductor device according to the present embodiment can include two or more adjacent layers In this case, these adjacent layers can be layers disposed below and above oxide semiconductor film 14.

For example, in semiconductor device 10 shown in FIG. 1A and FIG. 1B, gate insulating film 13 may be the amorphous adjacent layer. In semiconductor device 20 shown in FIG. 2, gate insulating film 13 and/or etch stopper layer 17 may be the amorphous adjacent layer(s). In semiconductor device 30 shown in FIG. 3, gate insulating film 13 and/or passivation film 18 may be the amorphous adjacent layer(s).

The amorphous adjacent layer is preferably an oxide layer including at least one of silicon and aluminum. In order to improve the field effect mobility as well as the reliability under irradiation of light in the semiconductor device, it is advantageous that the amorphous adjacent layer is an oxide layer including at least one of silicon and aluminum. Particularly, it is advantageous in providing a semiconductor device that can maintain high field effect mobility even if the temperature in the above-described heating is high. Moreover, when the amorphous adjacent layer is an oxide layer including at least one of silicon and aluminum, it can be advantageous in reducing off current. Examples of the oxide including at least one of silicon and aluminum can include, but not particularly limited to, silicon oxide (SiO_(x)), aluminum oxide (Al_(m)O_(n)), and the like.

Next, the following describes methods of producing the semiconductor devices according to the present embodiment. Each of the methods of producing the semiconductor devices includes the steps of: preparing the sputtering target of the foregoing embodiment; and forming the oxide semiconductor film by the sputtering method using this sputtering target. First, a method of producing semiconductor device 10 shown in FIG. 1A and FIG. 1B will be described. Although this production method should not be particularly limited, in order to efficiently produce semiconductor device 10 having high characteristics, with reference to FIG. 4A to FIG. 4D, the production method preferably includes the steps of forming gate electrode 12 on substrate 11 (FIG. 4A); forming gate insulating film 13 as an insulating layer on gate electrode 12 and substrate 11 (FIG. 4B); forming oxide semiconductor film 14 as a channel layer on gate insulating film 13 (FIG. 4C); and forming source electrode 15 and drain electrode 16 on oxide semiconductor film 14 not to be in contact with each other (FIG. 4D).

(1) Step of Forming Gate Electrode

With reference to FIG. 4A, gate electrode 12 is formed on substrate 11. Although substrate 11 should not be particularly limited, substrate 11 is preferably a quartz glass substrate, a non-alkali glass substrate, an alkaline glass substrate, or the like in order to increase transparency, price stability, and surface smoothness. Although gate electrode 12 should not be particularly limited, gate electrode 12 is preferably a Mo electrode, a Ti electrode, a W electrode, an Al electrode, a Cu electrode, or the like because these electrodes have high oxidation resistances and low electric resistances. Although the method of forming gate electrode 12 should not be particularly limited, the method of forming gate electrode 12 is preferably a vacuum deposition method, the sputtering method, or the like because a large area of gate electrode 12 can be uniformly formed on the main surface of substrate 11 by these methods. When gate electrode 12 is partially formed on the surface of substrate 11 as shown in FIG. 4A, an etching method employing a photoresist can be used.

(2) Step of Forming Gate Insulating Film

With reference to FIG. 4B, gate insulating film 13 is formed as an insulating layer on gate electrode 12 and substrate 11. Although a method of forming gate insulating film 13 should not be particularly limited, the method of forming gate insulating film 13 is preferably a plasma CVD (chemical vapor deposition) method or the like because a large area of gate insulating film 13 can be uniformly formed and an insulating property can be secured by the plasma CVD method.

Although the material of gate insulating film 13 should not be particularly limited, the material of gate insulating film 13 is preferably silicon oxide (SiO_(x)), silicon nitride (SiN_(y)), or the like in view of the insulating property. Moreover, when gate insulating film 13 is configured as the above-described amorphous adjacent layer, gate insulating film 13 is preferably an oxide including at least one of silicon and aluminum, such as silicon oxide (SiO_(x)) or aluminum oxide (Al_(m)O_(n)).

(3) Step of Forming Oxide Semiconductor Film

With reference to FIG. 4C, oxide semiconductor film 14 is formed as a channel layer on gate insulating film 13. As described above, oxide semiconductor film 14 is preferably formed by the step of forming oxide semiconductor film 14 by the sputtering method, and is preferably heated after forming the film by the sputtering method or is preferably heated while forming the film by the sputtering method, for example. As the source target (sputtering target) for the sputtering method, the oxide sintered material of the first embodiment above is used.

In order to obtain high reliability under irradiation of light, heating is preferably performed after forming the film by the sputtering method. In this case, heating may be performed immediately after forming oxide semiconductor film 14, or may be performed after forming source electrode 15, drain electrode 16, etch stopper layer 17, passivation layer 18, or the like. In order to obtain high reliability under irradiation of light, it is more preferable to perform the heating after forming etch stopper layer 17. If the heating is performed after forming etch stopper layer 17, this heating may be performed before or after forming source electrode 15 and drain electrode 16, but is preferably performed before forming passivation layer 18.

(4) Step of Forming Source Electrode and Drain Electrode

With reference to FIG. 4D, source electrode 15 and drain electrode 16 are formed on oxide semiconductor film 14 not to be in contact with each other. Although source electrode 15 and drain electrode 16 should not be particularly limited, each of source electrode 15 and drain electrode 16 is preferably a Mo electrode, a Ti electrode, a W electrode, an Al electrode, a Cu electrode, or the like because these electrodes have high oxidation resistances, low electric resistances, and low contact electric resistances with respect to oxide semiconductor film 14. Although a method of forming source electrode 15 and drain electrode 16 should not be particularly limited, the method of forming source electrode 15 and drain electrode 16 is preferably the vacuum deposition method, the sputtering method, or the like because large areas of source electrode 15 and drain electrode 16 can be uniformly formed on the main surface of substrate 11 having oxide semiconductor film 14 formed thereon. Although a method of forming source electrode 15 and drain electrode 16 not to be in contact with each other should not be particularly limited, the method of forming source electrode 15 and drain electrode 16 not to be in contact with each other is preferably formation using an etching method employing a photoresist because large areas of uniform patterns of source electrode 15 and drain electrode 16 can be formed by the etching method.

Next, a method of producing semiconductor device 20 shown in FIG. 2 will be described. This production method can be the same as the method of producing semiconductor device 10 shown in FIG. 1A and FIG. 1B except that this production method further includes the steps of: forming etch stopper layer 17 provided with contact hole 17 a; and forming passivation film 18. Specifically, with reference to FIG. 4A to FIG. 4D and FIG. 5A to FIG. 5D, the method of producing semiconductor device 20 includes the steps of: forming gate electrode 12 on substrate 11 (FIG. 4A); forming gate insulating film 13 as an insulating layer on gate electrode 12 and substrate 11 (FIG. 4B); forming oxide semiconductor film 14 as a channel layer on gate insulating film 13 (FIG. 4C); forming etch stopper layer 17 on oxide semiconductor film 14 and gate insulating film 13 (FIG. 5A); forming contact hole 17 a in etch stopper layer 17 (FIG. 5B); forming source electrode 15 and drain electrode 16 on oxide semiconductor film 14 and etch stopper layer 17 not to be in contact with each other (FIG. 5C); and forming passivation film 18 on etch stopper layer 17, source electrode 15, and drain electrode 16 (FIG. 5D).

Although the material of etch stopper layer 17 should not be particularly limited, the material of etch stopper layer 17 is preferably silicon oxide (SiO_(x)), silicon nitride (SiN_(y)), aluminum oxide (Al_(m)O_(n)), or the like in view of the insulating property. Moreover, when etch stopper layer 17 is configured as the above-described amorphous adjacent layer, etch stopper layer 17 is preferably an oxide including at least one of silicon and aluminum, such as silicon oxide (SiO_(x)) or aluminum oxide (Al_(m)O_(n)). Etch stopper layer 17 may be a combination of films composed of different materials Although a method of forming etch stopper layer 17 should not be particularly limited, the method of forming etch stopper layer 17 is preferably the plasma CVD (chemical vapor deposition) method, the sputtering method, the vacuum deposition method, or the like because a large area of etch stopper layer 17 can be uniformly formed and an insulating property can be secured by these methods.

Since source electrode 15 and drain electrode 16 need to be in contact with oxide semiconductor film 14, contact hole 17 a is formed in etch stopper layer 17 after forming etch stopper layer 17 on oxide semiconductor film 14 (FIG. 5B). Examples of a method of forming contact hole 17 a can include dry etching or wet etching. By etching etch stopper layer 17 by such a method to form contact hole 17 a, the surface of oxide semiconductor film 14 is exposed at the etched portion.

In the method of producing semiconductor device 20 shown in FIG. 2, as with the method of producing semiconductor device 10 shown in FIG. 1A and FIG. 1B, source electrode 15 and drain electrode 16 are formed on oxide semiconductor film 14 and etch stopper layer 17 not to be in contact with each other (FIG. 5C), and then passivation film 18 is formed on etch stopper layer 17, source electrode 15, and drain electrode 16 (FIG. 5D).

Although the material of passivation film 18 should not be particularly limited, the material of passivation film 18 is preferably silicon oxide (SiO_(x)), silicon nitride (SiN_(y)), aluminum oxide (Al_(m)O_(n)) or the like in view of the insulating property. Moreover, when passivation film 18 is configured as the above-described amorphous adjacent layer, passivation film 18 is preferably an oxide including at least one of silicon and aluminum such as silicon oxide (SiO_(x)) or aluminum oxide (Al_(m)O_(n)). Passivation film 18 may be a combination of films composed of different materials. Although a method of forming passivation film 18 should not be particularly limited, the method of forming passivation film 18 is preferably the plasma CVD (chemical vapor deposition) method, the sputtering method, the vacuum deposition method, or the like because a large area of passivation film 18 can be uniformly formed and an insulating property is secured by these methods

Moreover, as in semiconductor device 30 shown in FIG. 3, a back channel etch (BCE) structure may be employed without forming etch stopper layer 17 and passivation film 18 may be formed directly on gate insulating film 13, oxide semiconductor film 14, source electrode 15, and drain electrode 16. For passivation film 18 in this case, reference is made to the above description regarding passivation film 18 included in semiconductor device 20 shown in FIG. 2.

(5) Other Step

Finally, heating is normally performed. The heating can be performed by heating the substrate. The substrate temperature is preferably more than or equal to 100° C. and less than or equal to 250° C. The heating may be performed in a various types of atmospheres such as atmospheric air, nitrogen gas, nitrogen gas-oxygen gas, Ar gas, Ar-oxygen gas, water-vapor-containing atmospheric air, and water-vapor-containing nitrogen. Preferably, the atmosphere of the heating is a nitrogen or inert atmosphere such as Ar gas. A pressure of the atmosphere can be an atmospheric pressure, a reduced pressure (for example, less than 0.1 Pa), or an increased pressure (for example, 0.1 Pa to 9 MPa), but is preferably the atmospheric pressure. The heating time can be, for example, about 3 minutes to 2 hours, and is preferably about 10 minutes to 90 minutes

EXAMPLES Example 1 to Example 22

-   -   (1) Production of Oxide Sintered Material

(1-1) Preparation of Source Powders

The following powders were prepared: a tungsten oxide powder (denoted as “W” in Table 1) having composition and median particle size d50 (denoted as “W Particle Size” in Table 1) shown in Table 1 and having a purity of 99.99 mass %; a ZnO powder (denoted as “Z” in Table 1) having a median particle size d50 of 1.0 μm and having a purity of 99.99 mass %; and an In₂O₃ powder (denoted as “1” in Table 1) having a median particle size d50 of 1.0 μm and having a purity of 99.99 mass %.

(1-2) Preparation of Primary Mixture of Source Powders

From the source powders thus prepared, the tungsten oxide powder and the ZnO powder or the tungsten oxide powder and the indium oxide powder were first introduced into a ball mill and were pulverized and mixed for 18 hours, thereby preparing a primary mixture of the source powders. The tungsten oxide powder and the ZnO powder were mixed at about the following molar mixing ratio: tungsten oxide powder:ZnO powder=1:1. The tungsten oxide powder and the indium oxide powder were mixed at about the following molar mixture ratio: tungsten oxide powder:In₂O₃ powder=1:3. During the pulverization and mixing, ethanol was used as a dispersion medium. The obtained primary mixture of the source powders was dried in the atmospheric air.

(1-3) Formation of Calcinated Powder by Heating Primary Mixture

Next, the obtained primary mixture of the source powders was introduced into a crucible composed of alumina, and was calcinated in an air atmosphere for 8 hours at a calcination temperature shown in Table 1, thereby obtaining a calcinated powder composed of the ZnWO₄ type crystal phase or a calcinated powder composed of the In₆WO₁₂ type crystal phase. The composition (type) of the crystal phase in the obtained calcinated powder is shown in Table 1. In each of Examples 7 to 14, the following two types of calcinated powders were produced and used: a calcined powder composed of the ZnWO₄ type crystal phase; and a calcinated powder composed of the In₆WO₁₂ type crystal phase.

(1-4) Preparation of Secondary Mixture of Source Powders Including Calcinated Powder

Next, the obtained calcinated powder was introduced into a pot together with the remainder of the prepared source powders, i.e., the In₂O₃ powder or the ZnO powder, which were then introduced into a pulverization-mixing ball mill and were pulverized and mixed for 12 hours. In this way, a secondary mixture of the source powders was prepared. A mixture ratio of these powders was set to achieve a molar ratio of W, Zn, and In in the mixture as shown in Table 1. During the pulverization and mixing, ethanol was used as a dispersion medium. The obtained powder mixture was dried by spray dry.

(1-5) Formation of Molded Body by Molding Secondary Mixture

Next, the obtained secondary mixture was molded using a press, and was molded by CIP in still water of a room temperature (5° C. to 30° C.) under a pressure of 190 MPa, thereby obtaining a disk-like molded body having a diameter of 100 mm and a thickness of about 9 mm.

(1-6) Formation of Oxide Sintered Material by Sintering Molded Body

Next, the obtained molded body was sintered under an atmospheric pressure in an air atmosphere for 8 hours at a sintering temperature shown in Table 1, thereby obtaining an oxide sintered material including a first crystal phase including a bixbyite type crystal phase (In₂O₃ type phase) in which tungsten and zinc are dissolved in a solid state. Tungsten and zinc are determined to be dissolved in a solid state based on confirming that a peak location is displaced from the peak location defined in 6-0416 of the JCPDS card in X-ray diffraction measurement.

(1-7) Evaluation on Physical Properties of Oxide Sintered Material

[A] Identification of First Crystal Phase, Second Crystal Phase, and Fourth Crystal Phase

A sample was extracted from a portion of the oxide sintered material, and was subjected to crystal analysis by powder X-ray diffractometry, thereby confirming existence/non-existence of the bixbyite type crystal phase, the second crystal phase having the first diffraction peak at the location of more than 34.74 deg and less than 34.97 deg of 2θ, and the fourth crystal phase having the second diffraction peak at the location of more than 31.77 deg and less than 32.00 deg of 2θ. Measurement conditions for the X-ray diffraction were as follows.

(Measurement Conditions for X-Ray Diffraction)

0-2θ method,

X-ray source: Cu Kα rays,

X-ray tube voltage: 45 kV,

X-ray tube current: 40 mA,

Step width: 0.03 deg,

Step time: 1 second/step,

Measurement range 2θ: 10 deg to 90 deg.

Each of the oxide sintered materials of the Examples had the bixbyite type crystal phase, the second crystal phase, and the fourth crystal phase. Table 2 shows an angle of the first diffraction peak of the second crystal phase and an angle of the second diffraction peak of the fourth crystal phase. Moreover, a ratio IIn/Im was more than or equal to 3.0, where IIn represents the peak intensity of a diffraction peak, which has the highest intensity among diffraction peaks belonging to the bixbyite type crystal phase in the X-ray diffraction, and Im represents the peak intensity of a diffraction peak, which has the highest intensity among diffraction peaks not belonging to the bixbyite type crystal phase. Hence, it can be said that the bixbyite type crystal phase is a main component of each of the oxide sintered materials of the Examples.

[B] Confirmation of First Crystal Phase Being Main Component and Measurement of High-Content Indium Type Crystal Phase Ratio

A sample was extracted from a portion of the oxide sintered material and a surface of this sample was polished to be smooth. Next, SEM-EDX (Scanning Secondary Electron Microscope with Energy Dispersive X-Ray Fluorescent Emission Spectrometer) was employed to observe the surface of the sample by SEM (Scanning Secondary Electron Microscope) and analyze a composition ratio of metallic elements in each crystal particle by EDX (Energy Dispersive X-Ray Fluorescent Emission Spectrometer). Then, based on a tendency of the composition ratios of the metallic elements in those crystal particles, the crystal particles were classified into groups. Specifically, the crystal particles were classified into: a group A of crystal particles containing Zn, more typically, having a higher Zn content (content (atom %) of Zn relative to a total of In, W, and Zn) than that of a below-described group B; and group B of crystal particles having a very low Zn content or containing no Zn and having a higher In content (content (atom %) of In relative to the total of In, W. and Zn) than that of group A (high-content indium type crystal phase). It was determined that each of the crystal particles of group B was of the first crystal phase.

The “high-content indium type crystal phase ratio” in the oxide sintered material was defined as a ratio (percentage) of an area of the high-content indium type crystal phase (group B) in the surface of the oxide sintered material for which the above-described measurement had been performed. The high-content indium type crystal phase ratio of each of the oxide sintered materials of the Examples was more than or equal to 50%, and the first crystal phase was the main component.

[C] Measurement of Ratio Ia/Ib of Peak Intensity Ia of First Diffraction Peak to Peak Intensity Ib of Second Diffraction Peak

Based on the result of the X-ray diffraction measurement for identifying the first crystal phase, the second crystal phase, and the fourth crystal phase in [A] above, la and Ib were measured in accordance with the above-described formulas, and Ia/Ib was calculated. The result is shown in Table 2.

[D] Confirmation of Existence of Third Crystal Phase and Measurement of Average Major Axis Size and Average Aspect Ratio of Crystal Particles Included in Third Crystal Phase

In the confirmation of the first crystal phase being the main component and the measurement of the high-content indium type crystal phase ratio in [B] above, the crystal phase classified as group A was determined to be the third crystal phase. Moreover, in the SEM observation during the surface analysis, a reflection electron image of ×500 was measured, the average major axis size and average aspect ratio of the crystal particles included in the third crystal phase observed in deeper gray than group B classified as the first crystal phase were measured in accordance with the above-described method. The result is shown in Table 2.

[E] Confirmation of Existence of Fifth Crystal Phase, Indium Tungstate Compound Crystal Phase, Hexagonal Wurtzite Type Crystal Phase, and In₂O₃(ZnO)₅

In the measurement of the X-ray diffraction in [A] above, it was confirmed whether or not there are the fifth crystal phase, the indium tungstate compound crystal phase, the hexagonal wurtzite type crystal phase, and In₂O₃(ZnO)₅. In each of the Examples and Comparative Examples, existence of the indium tungstate compound crystal phase and the hexagonal wurtzite type crystal phase was not confirmed.

In the column “Identified Crystal Phase” in Table 2, the crystal phases existing in the oxide sintered material were collectively shown. Regarding the crystal phases, abbreviations in Table 2 are intended to indicate below-described crystal phases. It should be noted that the column “Identified Crystal Phase” in Table 2 indicates crystal phases that could be identified by the X-ray diffraction measurement (it should be noted that the second crystal phase and the fourth crystal phase identified in the X-ray diffraction measurement as described in [A] above are not shown), and is not intended to mean that the oxide sintered materials consist only of the crystal phases described in the column “Identified Crystal Phase”.

1: Bixbyite type crystal phase (first crystal phase)

ZW: Zinc tungstate compound crystal phase (third crystal phase and fifth crystal phase)

IZ: In₂O₃(ZnO)₅ (third crystal phase).

[F] Measurement of Contents of In, Zn, and W in Oxide Sintered Material

The contents of In, Zn, and W in the obtained oxide sintered material were measured by the ICP mass analysis method. Based on these contents, the W content (atom %), Zn content (atom %), and Zn/W ratio (atomic ratio) of the oxide sintered material were calculated. The result is shown in Table 2.

[G] Measurement of Apparent Density of Oxide Sintered Material

The apparent density of the obtained oxide sintered material was determined by an Archimedes method.

Comparative Examples 1 to 4

Each of oxide sintered materials was produced by the same method as those of the Examples except that the mixture ratio of the tungsten oxide powder, the ZnO powder, and the In₂O₃ powder, which were the source powders, was set as shown in Table 1 and except that these source powders were mixed at once without forming the calcinated powder and were sintered at a temperature shown in Table 1. Then, the obtained oxide sintered materials were subjected to evaluation of physical properties. Regarding the oxide sintered material of Comparative Example 3, the particles of the third crystal phase were not dispersed in the high-content indium type crystal phase and were in contact with each other, with the result that the shapes of the particles of the third crystal phase could not be specified. Accordingly, the average major axis size and average aspect ratio thereof could not be measured. In each of the Comparative Examples, the sintering temperature needed to be higher than that in each of the Examples in order to increase the apparent density Oxide sintered materials were produced in the same manner as in Comparative Examples 1 to 4 except that the sintering temperature was set at 1170° C., and the apparent density of each of these oxide sintered materials was 6.3 g/cm³.

(2) Production of Sputtering Target

(2-1) Production of Sputtering Target

Each of the obtained oxide sintered materials was processed to have the following size: 3 inches (76.2 mm) in diameter×6 mm in thickness. Then, each of the obtained oxide sintered materials was attached to a copper backing plate using an indium metal

(2-2) Measurement of Surface Roughness of Sputtering Target

Each of the produced sputtering targets was placed in a film formation chamber of a sputtering apparatus (not shown). The sputtering target was water-cooled via the copper backing plate. As a substrate, a mirror-surface Si wafer having a size of 2 inches was set to face the sputtering target. With the film formation chamber being set to have a vacuum of about 6×10⁻⁵ Pa, the target was sputtered as follows.

In a state in which a shutter was placed between the target and the substrate, a mixed gas of Ar (argon) gas and O₂ (oxygen) gas was introduced into the film formation chamber until the pressure therein reached 0.5 Pa. An O₂ gas content in the mixed gas was 25 volume %. DC power of 250 W was applied to the target to cause sputtering discharge. The sputtering was performed for 20 hours. Accordingly, a processing mark of the target surface is eliminated, thus resulting in a surface roughness during sputtering. The sputtering may be performed continuously or intermittently for 20 hours.

After ending the above operation, the target was removed from the vacuum chamber so as to measure an arithmetic mean roughness Ra in the sputtered target surface in accordance with JIS B 0601:2013 using a probe type surface roughness meter (“SURFCOM 480B” provided by Tokyo Seimitsu). The sputtered target surface refers to a portion of an etching mark, which is called “erosion”, in the form of a track corresponding to a magnetic field design of a magnet installed in a sputtering evaporation source. The measurement was performed in a direction along the width of the track under conditions that the center of the width of the track was regarded as a measurement center position and the measurement width was set to 0.4 mm. Obtained results are shown in Table 2 as relative values with the arithmetic mean roughness of Comparative Example 1 being regarded as “1”.

TABLE 1 Source Powder Molar Mixture Ratio W Particle Calcination Calcinated Sintering W Z I W Size Temperature Complex Oxide Temperature (%) (%) (%) Composition μm ° C. Type ° C. Example 1 0.03 31.93 68.04 WO₂ 1.2 850 In₆WO₁₂ 1170 Example 2 0.13 31.91 67.95 WO₂ 1.2 850 In₆WO₁₂ 1170 Example 3 0.15 52.90 46.95 WO₂ 1.2 850 In₆WO₁₂ 1170 Example 4 0.16 41.24 58.60 WO₂ 1.2 850 In₆WO₁₂ 1170 Example 5 0.17 31.91 67.92 WO₂ 1.2 850 In₆WO₁₂ 1170 Example 6 0.67 31.83 67.50 WO₂ 1.2 850 In₆WO₁₂ 1170 Example 7 1.18 3.50 95.32 WO_(2.72) 2.2 650 In₆WO₁₂, ZnWO₄ 1160 Example 8 1.81 19.78 78.41 WO₂ 2.5 650 In₆WO₁₂, ZnWO₄ 1160 Example 9 1.58 41.89 56.53 WO₃ 1.2 650 In₆WO₁₂, ZnWO₄ 1160 Example 10 1.45 53.72 44.83 WO₂ 1.1 650 In₆WO₁₂, ZnWO₄ 1160 Example 11 2.16 53.53 44.31 WO_(2.72) 0.9 650 In₆WO₁₂, ZnWO₄ 1160 Example 12 2.87 53.34 43.79 WO₃ 1.1 650 In₆WO₁₂, ZnWO₄ 1160 Example 13 4.26 52.97 42.77 WO_(2.72) 1.1 650 In₆WO₁₂, ZnWO₄ 1160 Example 14 6.71 57.41 35.88 WO₂ 0.9 650 In₆WO₁₂, ZnWO₄ 1160 Example 15 1.02 31.43 67.55 WO₂ 1.2 850 In₆WO₁₂ 1170 Example 16 1.90 10.89 87.21 WO_(2.72) 2.4 850 In₆WO₁₂ 1170 Example 17 1.68 32.32 66.00 WO₂ 1.2 850 In₆WO₁₂ 1170 Example 18 1.58 41.89 56.53 WO₃ 1.4 850 In₆WO₁₂ 1170 Example 19 2.25 47.87 49.88 WO₂ 0.9 850 In₆WO₁₂ 1170 Example 20 3.30 31.06 65.64 WO_(2.72) 0.8 850 In₆WO₁₂ 1170 Example 21 4.91 31.81 63.28 WO₃ 2.6 850 In₆WO₁₂ 1170 Example 22 8.03 31.32 60.65 WO₂ 3.0 850 In₆WO₁₂ 1170 Comparative 0.07 35.93 64.00 WO₃ 4.0 — — 1200 Example 1 Comparative 12.11 34.16 53.73 WO₃ 4.0 — — 1200 Example 2 Comparative 3.28 74.51 22.21 WO₃ 4.0 — — 1200 Example 3 Comparative 3.96 5.96 90.08 WO₃ 4.0 — — 1200 Example 4

TABLE 2 Oxide Sintered Material First Second Average Target Diffraction Diffraction Major Zn/W Arithmetic Peak Peak Axis Average Identified W Zn Ratio Apparent Mean 2θ 2θ Size Aspect Crystal Content Content (atomic Density Roughness deg deg Ia/Ib μm Ratio Phase (atom %) (atom %) ratio) (g/cm³) Ra Example 1 34.74 31.98 0.07 22 24 I, IZ 0.02 19.0 950 6.9 0.71 Example 2 34.75 31.98 0.12 22 23 I, IZ 0.08 19.0 238 6.8 0.63 Example 3 34.75 31.98 0.20 35 31 I, IZ 0.10 36.0 360 6.8 0.55 Example 4 34.75 31.92 0.20 26 27 I, IZ 0.10 26.0 260 6.8 0.50 Example 5 34.75 31.97 0.20 22 22 I, IZ 0.10 19.0 190 6.8 0.45 Example 6 34.75 31.97 0.25 22 23 I, IZ 0.40 19.0 47.5 6.9 0.42 Example 7 34.75 31.96 0.28 7 7 I, IZ, ZW 0.60 2.4 4.0 6.9 0.43 Example 8 34.78 31.95 1.58 21 23 I, IZ, ZW 1.10 11.0 10.0 6.8 0.53 Example 9 34.83 31.86 2.13 38 39 I, IZ, ZW 1.10 36.0 32.7 6.8 0.56 Example 10 34.87 31.87 2.15 38 39 I, IZ, ZW 1.10 36.0 32.7 6.8 0.63 Example 11 34.89 31.84 2.22 36 36 I, IZ, ZW 1.60 36.0 22.5 6.8 0.71 Example 12 34.93 31.85 2.18 35 32 I, IZ, ZW 2.10 36.0 17.1 6.8 0.76 Example 13 34.92 31.83 2.28 28 29 I, IZ, ZW 3.10 36.0 11.6 6.8 0.83 Example 14 34.96 31.86 2.31 36 39 I, IZ, ZW 5.00 41.0 8.2 6.8 0.83 Example 15 34.76 31.89 0.92 28 25 I, IZ, ZW 0.60 19.0 31.7 6.9 0.40 Example 16 34.78 31.94 0.93 8 6 I, IZ, ZW 1.00 6.0 6.0 7.0 0.50 Example 17 34.83 31.89 1.82 28 25 I, IZ, ZW 1.00 19.0 19.0 6.9 0.33 Example 18 34.83 31.91 1.71 25 24 I, IZ, ZW 1.00 26.0 26.0 6.7 0.50 Example 19 34.83 31.94 2.48 29 26 I, IZ, ZW 1.50 31.0 20.7 6.7 0.55 Example 20 34.83 31.95 1.00 18 16 I, IZ, ZW 2.00 19.0 9.5 6.9 0.40 Example 21 34.92 31.87 1.19 16 14 I, IZ, ZW 3.00 19.0 6.3 7.0 0.43 Example 22 34.96 31.78 0.91 14 5 I, IZ, ZW 5.00 19.0 3.8 7.1 0.47 Comparative None 31.90 — 23 20 I, IZ, ZW 0.01 19.0 1900 6.5 1.0 Example 1 Comparative None 31.88 — 8 6 I, IZ, ZW 7.00 19.0 2.7 6.6 1.3 Example 2 Comparative None 31.88 — Not Not I, IZ, ZW 1.00 55.0 55.0 6.6 1.6 Example 3 Measurable Measurable Comparative None None — 1 1 I, ZW 1.00 1.0 1.0 6.6 2.0 Example 4

(3) Production and Evaluation of Semiconductor Device (TFT) Including Oxide Semiconductor Film and Measurement of Surface Roughness of Oxide Semiconductor Film

(3-1) Production of Semiconductor Device (TFT) Including Oxide Semiconductor Film

A TFT having a configuration similar to that of semiconductor device 30 shown in FIG. 3 was produced in the following procedure. First, with reference to FIG. 4A, a synthetic quartz glass substrate having a size of 50 mm×50 mm×0.6 mm in thickness was prepared as substrate 11, and a Mo electrode having a thickness of 100 nm was formed as gate electrode 12 on substrate 11 by the sputtering method. Next, as shown in FIG. 4A, gate electrode 12 was etched using a photoresist to have a predetermined shape.

With reference to FIG. 4B, next, a SiO_(x) film serving as an amorphous oxide layer and having a thickness of 200 nm was formed as gate insulating film 13 on gate electrode 12 and substrate 11 by the plasma CVD method.

With reference to FIG. 4C, next, oxide semiconductor film 14 having a thickness of 25 nm was formed on gate insulating film 13 by the DC (direct current) magnetron sputtering method. A flat surface of the target with a diameter of 3 inches (76.2 mm) was a sputtering surface. As the target used, the oxide sintered material obtained above in (1) was used

The following more specifically describes the formation of oxide semiconductor film 14. Substrate 11 having gate electrode 12 and gate insulating film 13 formed thereon was disposed on a water-cooled substrate holder in the film formation chamber of the sputtering apparatus (not shown) such that gate insulating film 13 was exposed. The target was disposed to face gate insulating film 13 with a distance of 60 mm therebetween. With the film formation chamber being set to have a vacuum of about 6×10⁻⁵ Pa, the target was sputtered as follows.

First, in a state in which a shutter was placed between gate insulating film 13 and the target, a mixed gas of Ar (argon) gas and O₂ (oxygen) gas was introduced into the film formation chamber until the pressure therein reached 0.5 Pa. An O₂ gas content in the mixed gas was 25 volume %. DC power of 250 W was applied to cause sputtering discharge, thereby cleaning (pre-sputtering) the target surface for 5 minutes.

Next, under conditions that DC power of the same value was applied to the same target and the atmosphere in the film formation chamber was maintained to be unchanged, the above-described shutter was removed, thereby forming oxide semiconductor film 14 on gate insulating film 13. It should be noted that no bias voltage was particularly applied to the substrate holder. Moreover, the substrate holder was water-cooled or heated to adjust the temperature of substrate 11 during and after the film formation. Regarding examples accompanied with the description “Performed/120° C.” in the column “Heating during Film Formation” in Table 3 below among the Examples and the Comparative Examples, heating was performed simultaneously with the film formation by heating the substrate holder during the film formation to adjust the substrate temperature to 120° C. In this case, the heating time corresponds to the film formation time. Also in the case of performing heating simultaneously with the film formation, the substrate was heated at 250° C. for 10 minutes or at 350° C. for 10 minutes after the film formation (after the formation of the passivation layer as described below), and then semiconductor device characteristics described later were measured. On the other hand, in the case of “Not Performed” in the column “Heating during Film Formation” in Table 3 below among the Examples and the Comparative Examples, the substrate holder was water-cooled during the film formation to set the substrate temperature at about 20° C., and the substrate was heated at 250° C. for 10 minutes or at 350° C. for 10 minutes after the film formation (after the formation of the passivation layer as described below), and the semiconductor device characteristics described later were measured.

In the manner described above, oxide semiconductor film 14 was formed by the DC (direct current) magnetron sputtering method employing the target obtained by processing the oxide sintered material obtained above in (1). Oxide semiconductor film 14 served as a channel layer in the TFT. The film thickness of oxide semiconductor film 14 formed in each of the Examples and the Comparative Examples was 25 nm.

Next, oxide semiconductor film 14 thus formed were partially etched to form a source electrode formation portion 14 s, a drain electrode formation portion 14 d, and a channel portion 14 c. The size of the main surface of each of source electrode formation portion 14 s and drain electrode formation portion 14 d was set at 50 μm×50 μm, channel length C_(L) thereof was set at 30 μm (with reference to FIG. 1A and FIG. 1B, channel length C_(L) refers to a distance of channel portion 14 c between source electrode 15 and drain electrode 16), and channel width C_(W) thereof was set at 40 μm (with reference to FIG. 1A and FIG. 1B, channel width C_(W) refers to the width of channel portion 14 c). 25 (at the longitudinal side)×25 (at the lateral side) of channel portions 14 c were disposed at an interval of 3 mm within the substrate main surface of 75 mm×75 mm such that 25 (at the longitudinal side)×25 (at the lateral side) of TFTs were disposed at an interval of 3 mm within the substrate main surface of 75 mm×75 mm.

Oxide semiconductor film 14 was partially etched in the following manner: substrate 11 having gate electrode 12, gate insulating film 13, and oxide semiconductor film 14 formed thereon in this order was immersed, at 40° C., in an etching aqueous solution prepared to have a volume ratio of oxalic acid:water=5:95.

With reference to FIG. 4D, source electrode 15 and drain electrode 16 are then formed on oxide semiconductor film 14 to be separated from each other.

Specifically, first, a resist (not shown) was applied onto oxide semiconductor film 14, was exposed to light and was developed to expose only the respective main surfaces of source electrode formation portion 14 s and drain electrode formation portion 14 d of oxide semiconductor film 14. Next, the sputtering method was employed to form Mo electrodes each having a thickness of 100 nm and respectively serving as source electrode 15 and drain electrode 16 on the main surfaces of source electrode formation portion 14 s and drain electrode formation portion 14 d of oxide semiconductor film 14. Then, the resist on oxide semiconductor film 14 was removed. One Mo electrode serving as source electrode 15 and one Mo electrode serving as drain electrode 16 are disposed for one channel portion 14 c such that 25 (at the longitudinal side)×25 (at the lateral side) of TFTs were disposed at an interval of 3 mm within the substrate main surface of 75 mm×75 mm.

Next, with reference to FIG. 3, passivation film 18 was formed on gate insulating film 13, oxide semiconductor film 14, source electrode 15, and drain electrode 16. Passivation film 18 had a configuration obtained by forming a SiO_(x) film, which served as an amorphous oxide layer and had a thickness of 200 nm, by the plasma CVD method and then forming a SiN_(y) film having a thickness of 200 nm by the plasma CVD method on the SiO_(x) film. Alternatively, passivation film 18 had a configuration obtained by forming an Al_(m)O_(n) film, which served as an amorphous oxide layer and had a thickness of 120 nm, by the sputtering method and then forming a SiN_(y) film having a thickness of 200 nm on the Al_(m)On film by the plasma CVD method. When the amorphous oxide layer is the SiO_(x) film, the column “PV Layer” in Table 3 below indicates “SiO_(x)”, whereas when the amorphous oxide layer is the Al_(m)O_(n) film, the column “PV Layer” indicates “Al_(m)O_(n)”. In order to improve reliability under irradiation of light, in an atomic composition ratio of the SiO, film, an oxygen content is desirably closer to that in Si:O=1:2, whereas in an atomic composition ratio of the Al_(m)O_(n) film, an oxygen content is desirably closer to that in Al:O=2:3.

Next, passivation film 18 on source electrode 15 and drain electrode 16 was etched by reactive ion etching to form a contact hole, thereby exposing portions of the surfaces of source electrode 15 and drain electrode 16.

Finally, heating was performed in a nitrogen atmosphere under an atmospheric pressure. This heating was performed in all the Examples and Comparative Examples, specifically, the heating was performed at 250° C. for 10 minutes in the nitrogen atmosphere or at 350° C. for 10 minutes in the nitrogen atmosphere. In this way, a TFT including oxide semiconductor film 14 as a channel layer was obtained.

(3-2) Crystallinity, W Content, Zn Content, and Zn/W Ratio of Oxide Semiconductor Film

The crystallinity of oxide semiconductor film 14 included in the produced TFT was evaluated in accordance with the above-described measurement method and definition. The column “Crystallinity” in Table 3 describes “Nano Crystal” in the case of the nano crystal, and describes “Amorphous” in the case of amorphous. Moreover, the respective contents of In, W, and Zn in oxide semiconductor film 14 were measured by RBS (Rutherford Backscattering Spectrometry). Based on these contents, the W content (atom %), Zn content (atom %), and Zn/W ratio (atomic ratio) of oxide semiconductor film 14 were determined. Results thereof are shown in Table 3.

(3-3) Production of Oxide Semiconductor Film and Measurement of Surface Roughness Thereof

A sputtering target was produced in accordance with the process described above in (2-1). Next, sputtering was performed for 20 hours in the same manner as described above in (2-2). Next, a mirror-surface Si wafer having a size of 2 inches was set to face the sputtering target. With the film formation chamber being set to have a vacuum of about 6×10′⁵ Pa, the target was sputtered as follows. In a state in which a shutter was placed between the target and the substrate, a mixed gas of Ar (argon) gas and O₂ (oxygen) gas was introduced into the film formation chamber until the pressure therein reached 0.5 Pa. An O₂ gas content in the mixed gas was 25 volume %. DC power of 250 W was applied to the target to cause sputtering discharge. After holding for 10 minutes, the shutter was removed from between the substrate and the target so as to form an oxide semiconductor film on the substrate. Film formation time was adjusted such that the oxide semiconductor film has a film thickness of 2 μm.

After the film formation, cooling was performed for 10 minutes, and then the substrate was removed from the vacuum chamber so as to measure an arithmetic mean roughness Ra in the surface of the oxide semiconductor film at the central portion of the 2-inch Si wafer in accordance with JIS B 0601:2013 using a probe type surface roughness meter (“P-16” provided by KLA Tencor). Obtained results are shown in Table 3 as relative values with the arithmetic mean roughness of Comparative Example 1 being regarded as “1”.

(3-4) Evaluation on Characteristics of Semiconductor Device

The characteristics of the TFT serving as semiconductor device 10 were evaluated as follows. First, a measurement needle was brought into contact with each of gate electrode 12, source electrode 15, and drain electrode 16. A source-drain voltage V_(ds) of 0.2 V was applied between source electrode 15 and drain electrode 16, a source-gate voltage V, applied between source electrode 15 and gate electrode 12 was changed from −10 V to 15 V, and a source-drain current I_(ds) on this occasion was measured. Then, a relation between source-gate voltage V_(gs) and a square root ((I_(ds))^(1/2)) of source-drain current I_(ds) was illustrated in a graph (hereinafter, this graph is also referred to as “V_(gs)−(I_(ds))^(1/2) curve”). A threshold voltage V_(th) was represented by a point (x intercept) at which the x axis (V_(gs)) crossed a line tangential to a point at which inclination of a tangential line drawn to the V_(gs)−(I_(ds))^(1/2) curve was the maximum. Measurement of threshold voltage V_(th) was performed for: the TFT having been through heating at 250° C. for 10 minutes in the nitrogen atmosphere under the atmospheric pressure (V_(th) (250° C.)); and the TFT having been through heating at 350° C. for 10 minutes in the nitrogen atmosphere under the atmospheric pressure (V_(th) (350° C.)). It is considered that V_(th) is desirably more than or equal to 0 V, and is desirably closer to 1.0 V to conform to driving voltage for a-Si when the TFT is used for a display device.

Moreover, g_(m) was derived by differentiating source-drain current I_(ds) with respect to source-gate voltage V, in accordance with the following formula [a]:

g _(m) =dI _(ds) /dV _(gs)  [a].

Then, the value of g_(m) with V_(gs)=10.0 V was used to determine field effect mobility μ_(fe) based on the following formula [b]:

μ_(fe) =g _(m) ·C _(i)(C _(W) ·C _(i) ·V _(ds))[b].

In the above formula [b], channel length C₁, was 30 μm and channel width C_(W) was 40 μm. Moreover, capacitance C_(i) of gate insulating film 13 was set at 3.4×10⁻⁸ F/cm², and source-drain voltage V_(ds) was set at 0.5 V.

The column “Mobility (250° C.)” of Table 3 shows field effect mobility μ_(fe) after heating at 250° C. for 10 minutes in the nitrogen atmosphere under the atmospheric pressure. Moreover, the column “Mobility (350° C.)” of Table 3 shows field effect mobility μ_(fe) after heating at 350° C. for 10 minutes in the nitrogen atmosphere under the atmospheric pressure. As shown in Table 3, as the Zn/W ratio is larger, a difference between the mobility (250° C.) and the mobility (350° C.) tends to be smaller.

Further, the following reliability evaluation test under irradiation of light was performed. While irradiating with light having a wavelength of 460 nm with an intensity of 0.3 mW/cm² from above the TFT, source-gate voltage V, applied between source electrode 15 and gate electrode 12 was fixed to −25 V and was continued to be applied for 1 hour. After 1 s, 10 s, 100 s, 300 s and 3600 s from the start of the application, threshold voltage V_(th) was determined by the above-described method, and a difference ΔV_(th) was determined between maximum threshold voltage V_(th) and minimum threshold voltage V_(th). As ΔV_(th) is smaller, it is determined that reliability under irradiation of light is higher. The column “ΔV_(th) (250° C.)” of Table 3 shows ΔV_(th) after heating at 250° C. for 10 minutes in the nitrogen atmosphere under the atmospheric pressure. Moreover, the column “ΔV_(th) (350° C.)” of Table 3 shows ΔV_(th) after heating at 350° C. for 10 minutes in the nitrogen atmosphere under the atmospheric pressure. It should be noted that the semiconductor device of Comparative Example 1 was unable to be driven as a TFT.

TABLE 3 Oxide Semiconductor Film Zn/W W Zn Ratio Arithmetic Heating Content Content (atomic Mean Roughness during Film Crystallinity (atom %) (atom %) ratio) Ra Formation Example 1 Amorphous 0.03 18.0 600 0.92 Performed/120° C. Example 2 Amorphous 0.10 18.0 180 0.82 Performed/120° C. Example 3 Amorphous 0.20 35.0 175 0.71 Performed/120° C. Example 4 Amorphous 0.20 25.0 125 0.65 Performed/120° C. Example 5 Amorphous 0.20 18.0 90.0 0.59 Performed/120° C. Example 6 Amorphous 0.50 18.0 36.0 0.55 Performed/120° C. Example 7 Amorphous 0.70 2.0 2.9 0.56 Not Performed Example 8 Nano Crystal 1.00 10.0 10.0 0.69 Not Performed Example 9 Nano Crystal 1.00 31.0 31.0 0.73 Not Performed Example 10 Nano Crystal 1.00 31.0 31.0 0.82 Not Performed Example 11 Nano Crystal 1.50 34.0 23.0 0.92 Not Performed Example 12 Nano Crystal 2.00 34.0 17.0 0.99 Not Performed Example 13 Nano Crystal 3.00 34.0 11.0 1.08 Not Performed Example 14 Nano Crystal 5.00 39.0 7.8 1.08 Not Performed Example 15 Nano Crystal 0.60 18.0 30.0 0.52 Performed/120° C. Example 16 Amorphous 1.00 4.0 4.0 0.65 Performed/120° C. Example 17 Nano Crystal 1.00 17.0 17.0 0.43 Performed/120° C. Example 18 Nano Crystal 1.00 21.0 21.0 0.65 Performed/120° C. Example 19 Nano Crystal 1.50 30.0 20.0 0.71 Performed/120° C. Example 20 Nano Crystal 2.00 17.0 8.5 0.52 Performed/120° C. Example 21 Nano Crystal 3.00 17.0 5.7 0.56 Performed/120° C. Example 22 Nano Crystal 5.00 17.0 3.4 0.61 Performed/120° C. Comparative Nano Crystal 0.01 17.0 1700 1 Performed/120° C. Example 1 Comparative Nano Crystal 1.60 17.0 11.0 14.3 Performed/120° C. Example 2 Comparative Nano Crystal 1.60 51.0 32.0 41.6 Performed/120° C. Example 3 Comparative Nano Crystal 1.40 0.5 0.4 0.468 Performed/120° C. Example 4 Evaluation on Characteristics of Semiconductor Device Mobility Mobility V_(th) V_(th) ΔV_(th) ΔV_(th) PV (250° C.) (350° C.) (250° C.) (350° C.) (250° C.) (350° C.) Layer (cm²/Vs) (V) (V) Example 1 SiO_(x) 60 54 −9.6 −6.3 1.44 1.22 Example 2 SiO_(x) 56 50 −5.4 −4.2 1.86 1.54 Example 3 SiO_(x) 51 46 −4.7 −3.1 2.78 2.29 Example 4 SiO_(x) 48 46 −4.2 −2.8 2.56 2.11 Example 5 SiO_(x) 53 50 −4 −2 2.12 1.76 Example 6 SiO_(x) 47 46 −3.5 0 2.42 2.01 Example 7 Al_(m)O_(n) 40 18 −2.5 0.4 2.63 2.17 Example 8 Al_(m)O_(n) 33 30 −1.2 1.8 3.13 2.57 Example 9 Al_(m)O_(n) 32 30 −2.0 0.9 3.58 2.93 Example 10 Al_(m)O_(n) 31 28 −2.2 0.7 3.77 3.08 Example 11 Al_(m)O_(n) 30 27 −1.2 1.8 4.02 3.29 Example 12 Al_(m)O_(n) 26 25 −0.7 2.3 4.21 3.44 Example 13 Al_(m)O_(n) 23 21 0 2.6 4.83 3.93 Example 14 Al_(m)O_(n) 22 20 0.3 3.3 5.25 4.27 Example 15 SiO_(x) 45 44 −2.7 0.4 2.56 2.12 Example 16 SiO_(x) 46 14 −0.8 2.3 3.4 2.79 Example 17 SiO_(x) 40 38 −1.9 1.0 3.54 2.90 Example 18 SiO_(x) 39 38 −1.9 0.8 3.76 3.08 Example 19 SiO_(x) 36 35 −1.5 1.6 3.83 3.13 Example 20 SiO_(x) 33 31 −1.2 1.7 4.12 3.37 Example 21 SiO_(x) 30 30 0.1 2.6 4.54 3.70 Example 22 SiO_(x) 28 29 0.6 3.8 4.77 3.89 Comparative SiO_(x) Not Driven Example 1 Comparative SiO_(x) 30 28 −5.6 −5.4 7.2 5.83 Example 2 Comparative SiO_(x) 28 26 −8.8 −8.5 7.9 6.39 Example 3 Comparative SiO_(x) 32 9 −4.8 −4.8 6.4 5.19 Example 4

The embodiments and examples disclosed herein are illustrative and non-restrictive in any respect. The scope of the present invention is defined by the terms of the claims, rather than the embodiments and examples described above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

REFERENCE SIGNS LIST

10, 20, 30: semiconductor device (TFT); 11: substrate; 12: gate electrode; 13: gate insulating film; 14: oxide semiconductor film; 14 c: channel portion; 14 d: drain electrode formation portion; 14 s: source electrode formation portion; 15: source electrode; 16: drain electrode; 17: etch stopper layer; 17 a: contact hole; 18: passivation film. 

1. An oxide sintered material containing indium, tungsten, and zinc, the oxide sintered material comprising: a first crystal phase that is a main component of the oxide sintered material and includes a bixbyite type crystal phase; and a second crystal phase having a first diffraction peak at a location of more than 34.74 deg and less than 34.97 deg of 2θ in X-ray diffraction, wherein the oxide sintered material has an apparent density of more than 6.4 g/cm³ and less than or equal to 7.5 g/cm³, a content of the tungsten relative to a total of the indium, the tungsten, and the zinc in the oxide sintered material is more than 0.01 atom % and less than or equal to 5.0 atom %, a content of the zinc relative to the total of the indium, the tungsten, and the zinc in the oxide sintered material is more than or equal to 1.2 atom % and less than 50 atom %, and an atomic ratio of the zinc to the tungsten in the oxide sintered material is more than 1.0 and less than
 20000. 2. The oxide sintered material according to claim 1, further comprising a third crystal phase, which is a crystal phase different from the first crystal phase and contains the zinc, wherein the third crystal phase includes particles having an average major axis size of more than or equal to 3 μm and less than or equal to 50 μm and having an average aspect ratio of more than or equal to 1.5 and less than or equal to
 50. 3. The oxide sintered material according to claim 2, wherein the third crystal phase is dispersed in the first crystal phase.
 4. The oxide sintered material according to claim 2, wherein the third crystal phase includes a fourth crystal phase having a second diffraction peak at a location of more than 31.77 deg and less than 32.00 deg of 2θ in the X-ray diffraction.
 5. The oxide sintered material according to claim 4, wherein a ratio Ia/Ib of a peak intensity Ia of the first diffraction peak to a peak intensity Ib of the second diffraction peak is more than or equal to 0.05 and less than or equal to
 3. 6. The oxide sintered material according to claim 2, wherein the third crystal phase includes a fifth crystal phase, which is a zinc tungstate compound crystal phase.
 7. The oxide sintered material according to claim 1, wherein the first crystal phase further includes an indium tungstate compound crystal phase.
 8. A sputtering target comprising the oxide sintered material recited in claim
 1. 9. A method of producing a semiconductor device including an oxide semiconductor film, the method comprising: preparing the sputtering target recited in claim 8; and forming the oxide semiconductor film by a sputtering method using the sputtering target.
 10. The method of producing the semiconductor device according to claim 9, wherein a content of the tungsten relative to the total of the indium, the tungsten, and the zinc in the oxide semiconductor film is more than 0.01 atom % and less than or equal to 5.0 atom %, a content of the zinc relative to the total of the indium, the tungsten, and the zinc in the oxide semiconductor film is more than or equal to 1.2 atom % and less than 50 atom %, and an atomic ratio of the zinc to the tungsten in the oxide semiconductor film is more than 1.0 and less than
 20000. 11. The method of producing the semiconductor device according to claim 9, wherein the oxide semiconductor film is composed of at least one of a nano crystal oxide and an amorphous oxide.
 12. A method of producing the oxide sintered material recited in claim 1, the method comprising: preparing a primary mixture of an indium oxide powder and a tungsten oxide powder; forming a calcinated powder by heating the primary mixture; preparing a secondary mixture of source powders including the calcinated powder; forming a molded body by molding the secondary mixture; and forming an oxide sintered material by sintering the molded body, wherein the forming of the calcinated powder includes forming a powder of a complex oxide including indium and tungsten as the calcinated powder by heating the primary mixture at a temperature of more than or equal to 700° C. and less than 1400° C. in an oxygen-containing atmosphere.
 13. The method of producing the oxide sintered material according to claim 12, wherein the complex oxide includes an In₆WO₁₂ type crystal phase.
 14. A method of producing the oxide sintered material recited in claim 1, the method comprising: preparing a primary mixture of a zinc oxide powder and a tungsten oxide powder; forming a calcinated powder by heating the primary mixture; preparing a secondary mixture of source powders including the calcinated powder; forming a molded body by molding the secondary mixture; and forming an oxide sintered material by sintering the molded body, wherein the forming of the calcinated powder includes forming a powder of a complex oxide including zinc and tungsten as the calcinated powder by heating the primary mixture at a temperature of more than or equal to 550° C. and less than 1200° C. in an oxygen-containing atmosphere.
 15. The method of producing the oxide sintered material according to claim 14, wherein the complex oxide includes a ZnWO₄ type crystal phase.
 16. The method of producing the oxide sintered material according to claim 12, wherein the tungsten oxide powder includes at least one crystal phase selected from a group consisting of a WO₃ crystal phase, a WO₂ crystal phase, and a WO_(2.72) crystal phase.
 17. The method of producing the oxide sintered material according to claim 12, wherein the tungsten oxide powder has a median particle size d50 of more than or equal to 0.1 μm and less than or equal to 4 μm. 